EP2247398B1 - Phlegmatized metal powder or alloy powder and method and reaction vessel for the production thereof - Google Patents
Phlegmatized metal powder or alloy powder and method and reaction vessel for the production thereof Download PDFInfo
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- EP2247398B1 EP2247398B1 EP09703271.8A EP09703271A EP2247398B1 EP 2247398 B1 EP2247398 B1 EP 2247398B1 EP 09703271 A EP09703271 A EP 09703271A EP 2247398 B1 EP2247398 B1 EP 2247398B1
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- metal
- powder
- passivating
- metal powder
- alloy powder
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B19/00—Combinations of furnaces of kinds not covered by a single preceding main group
- F27B19/02—Combinations of furnaces of kinds not covered by a single preceding main group combined in one structure
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- 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
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- 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
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1277—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
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- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens, or the like for the charge within the furnace
- F27D5/0068—Containers
- F27D2005/0075—Pots, e.g. slag pots, ladles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the invention relates to the production of passivated, air-manageable finest metal powder of the elements zirconium, titanium and / or hafnium, having a mean particle size below 10 microns (measured by permeability methods such as the Blaine or Fisher method) by metallothermal reduction of their oxides by means of calcium and magnesium.
- hydrogen in an amount of at least 500 ppm and nitrogen in an amount of at least 1000 ppm are used as phlegmatizing additives, as phlegmatizing solid additives carbon, silicon, boron, nickel, chromium and aluminum in quantities of at least 2000 ppm.
- the oxides can be individually reduced to produce pure metal powders. However, they may also be reduced in admixture with each other or in admixture with metal powders and / or oxides of the elements nickel, chromium and aluminum to produce alloys of titanium, zirconium and hafnium with these elements.
- Metal-thermal reductions using calcium and magnesium as reducing agents are used to recover rare metals from their oxides when they are otherwise treated, for example, electrochemically from aqueous solutions, from molten salts or by reducing their oxides with carbon or with gases such as hydrogen or carbon monoxide are not or only in low purity to win.
- a typical industrial example of this is the production of rare earth metals such as yttrium, cerium, lanthanum and others and of the metal beryllium from their oxides or halides with magnesium, Calcium or aluminum [Römpps Chemie-Lexikon "Metallothermie"].
- the particle size of the metal powder to be obtained can be largely predetermined by the choice of the particle size of the corresponding metal oxide to be reduced [ Petrikeev, et al., Tsvetnye Met., No. 8 (1991) 71-72 ].
- the EP 1 644 544 B1 a process for producing metal powders or metal hydride powders, the elements Ti, Zr, Hf, V, Nb, Ta and Cr, in which an oxide of these elements is mixed with a reducing agent and this mixture is heated in a furnace, optionally under a hydrogen atmosphere, until the Reduction reaction begins, the reaction product is leached and then washed and dried, wherein the oxide used has an average particle size of 0.5 to 20 pm, a BET specific surface area of 0.5 to 20 m2 / g and a minimum content of 94Gew.- % having.
- the design of a suitable reaction vessel is not explained.
- the metal oxide of the reduction metal formed with the reduction should not form double oxides or other mixed oxides with the oxide to be reduced, because the yield is reduced by this parallel side reaction.
- the vapor pressure of the reducing metal at the expected reaction temperature usually 800 to 1400 ° C
- the reduction metal oxide formed in the reduction must be soluble in water or aqueous acids in order to be able to remove it from the reaction mass by leaching after completion of the reaction.
- the poor solubility of the oxides of silicon and aluminum as well as their tendency to form mixed oxides is the reason that these low-priced elements are often not used as a reducing agent.
- Metal-thermal reduction reactions are generally self-contained. This term refers to reactions that are initiated by an initial ignition and then automatically continue to run without external energy input.
- the initial ignition can be initiated chemically, electrically (by a filament or by induction) or simply by hot heating of a portion of the metal / metal oxide mixture [ DE PS 96317 ].
- a gas-fired crucible furnace has the advantage that the retort is heated quickly. At a temperature of about 100 to 450 ° C, depending on the grain sizes and the nature of the starting materials, sets an initial ignition, which starts at a hot spot, which is usually laterally in the lower third of the crucible in which the mixture to be reacted located.
- the temperature then rises within a few minutes to values between 900 ° C and 1200 ° C, depending on whether calcium or magnesium is used as the primary reducing metal.
- Calcium leads to higher than 1000 ° C, magnesium to slightly lower peak temperatures.
- the pressure inside the retort increases. When reaching an overpressure of about 50 to 100 mbar, therefore, a valve is opened and the pressure released, It is usually hydrogen, resulting from the moisture of the starting materials forms, magnesium metal vapor and alkali metal vapors from impurities of the starting materials. This can lead to a flame on the drain valve. Resulting vapors and dusts must be extracted at the place of their formation.
- the opening of the valve can be done manually, but also electromechanical or pneumatic, and it can be controlled for security reasons remotely, for example, under video observation.
- As relief valves for the overpressure primarily sealless plug valves or ball valves with a large cross section are used.
- Metal-thermal reductions continue to go on - when ignited - inexorably. Once initiated, the reaction can no longer be stopped using conventional processing techniques such as cooling or adding diluents.
- Example (1) If the metal-thermal reduction of zirconium in Example (1) were applied, for example in a ceramic container in air or under a slag cover similar to EP 05836701 B would run, so after the reaction on cooling of the reaction mass, the zirconium powder formed would reconnect with the oxygen in the air.
- Metallic titanium, zirconium, and hafnium, and alloys of these metals are only stable to air because they are surrounded by a dense, oxygen-impermeable, oxide or oxynitride envelope at room temperature, the so-called passive layer.
- the passivation is also known from many other metals, such as aluminum, zinc and chromium. Passivation occurs automatically on most metals. By contact of the metal surface with the oxygen and nitrogen of the air, with moisture and in air Carbon dioxide builds up the protective passive film without any special action. This is not so with the metals Ti, Zr and Hf and their alloys, when they are in fine powder form and produced in a protective atmosphere under argon, helium or in vacuum.
- the object of the present invention was therefore to provide a method and a reaction vessel for carrying out this process for the production of metal powders or alloy powders of the reactive metals zirconium, titanium or hafnium from the corresponding oxides or oxide mixtures, wherein the prepared reactive metal powders or alloy powders subsequently, For example, for the purpose of further processing, to be handled in the air.
- the process according to the invention allows the reduction reaction to be carried out under protective gases, such as argon or helium, or in vacuo, in order to prevent uncontrolled access of air and moisture.
- protective gases such as argon or helium, or in vacuo
- the construction of the reaction vessel further allows in particular the targeted addition of a measured amount of gases during and / or after the reduction reaction in order to specifically phlegmatize the metals or alloys formed and to influence their chemical behavior.
- the construction further permits the reduction of the oxides or oxide mixtures under a reactive gas atmosphere, especially under hydrogen, when it is intended to produce hydrides of the metals Ti, Zr and Hf. It also allows the hydrogenation of alloys made by fusion metallurgy, e.g.
- an alloy of 70% Zr and 30% nickel or titanium sponge by heating and introducing hydrogen.
- hydrogen in addition to hydrogen, ammonia, methane, carbon monoxide, carbon dioxide and nitrogen may also be introduced into the retort to produce hydrides, subhydrides, carbides, nitrides, hydride-nitride mixtures or oxynitrides of the metals zirconium, titanium and hafnium.
- the design incorporates a special flange and lid cooling design to prevent unwanted ingress of cooling water into the retort space.
- a special spacer with support ring allows the retort to be inserted at different depths into the combustion chamber of the reduction furnace.
- the reduction metal used is preferably calcium and / or magnesium. Calcium and magnesium can therefore be used individually or together. In principle, further additives, such as carbon, silicon or silicon oxide and other substances, can be added in order to influence the properties of the reactive metal powder produced during the reduction
- a passivating gas preferably nitrogen and / or hydrogen is introduced.
- At least 500 ppm of hydrogen and 1000 ppm of nitrogen should be present in the metal powders in order to avoid the above-mentioned reactions.
- the amount of hydrogen should be better at least 1000 ppm (0.1%), preferably 1000 to 2000 ppm, and nitrogen at least 2000 ppm (0.2%), preferably 2000 - 3000 ppm.
- Nitrogen and hydrogen can also be introduced in the form of ammonia.
- At least 2,000 ppm (0.2% by weight) and at most 30,000 ppm (3% by weight) of carbon, silicon, boron, nickel, chromium and / or aluminum can be introduced as passivating solids.
- the passivating solid can also be introduced in the form of a fine oxide of the elements Ni, Cr, Al, Si and B having an average particle size of less than 20 ⁇ m and reduced together with the metal oxide.
- carbon can be introduced via the gas phase in the form of methane, carbon dioxide or carbon monoxide.
- the passivating gases and solids can also be introduced together.
- the ignitability of the phlegmatized metal powders or alloy powders can be further reduced by washing out submicroscopic particles of less than 0.2 ⁇ m grain size during leaching and / or washing.
- a hypothetical idea of the inventor is the following: by the inclusion of the gases in the metal grid, the total energy level of the free electrons in the metal is lowered so far that the spontaneous reaction with oxygen under combustion or the reaction with water is omitted.
- wet-chemical preparation of the metal powders in water and acid only the actual, oxidic passive layer on the particle surface is formed by a slow oxidation reaction with atmospheric oxygen or by slow reaction with water. Since the metal powder is heated to room temperature or at most to the boiling point of the water in the wet-chemical processing, all diffusion processes are slow and it can now form a dense, firmly adhering "passive layer" of metal oxide (and metal nitride), the metal permanently protects against further oxidation.
- the effect of the incorporation of gases into the metal grid is to be exploited.
- Such incorporation is advantageously achieved precisely in that the phlegmatizing compounds are added in particular already during the reduction reaction.
- the degree of passivation is difficult to quantify, it can best be deduced from the ignition point of the metal powder in air.
- z.T. also standardized methods available.
- the metals Ti, Zr and Hf the following simple test arrangement is suitable: in a copper or steel cylinder with a diameter and a height of 70 mm each, a hole of 15 mm diameter and 35 mm depth is drilled in the middle. At a distance of 4 mm, a hole 5 mm thick, also 35 mm deep, is drilled to accommodate a thermocouple.
- the block is preheated uniformly to about 140 - 150 ° C, then an amount of 1 - 2 g of the metal powder to be tested is filled into the larger bore and it is heated further until ignition.
- This can be recognized optically (e.g., by video camera).
- By evaluating the time / temperature curve of the thermocouple you can determine the ignition point quite accurately. If the ignition points are below 150 ° C, one can not assume a safe passivation or phlegmatization. Metal powders with such low ignition points should be destroyed by burning in a safe place.
- the firing time also indicates the degree of phlegmatization.
- the method is described in Example 1. References to this can also be taken from measurements of the minimum electrical ignition energy, which however is very difficult to determine. [ Berger, B., Gyseler, J., Method for Testing the Sensitivity of Explosives to Electrostatic Discharge, Techn. Of Energetic Metals, 18th Ann. Conf. of ICT, Düsseldorf 1987, pp. 55/1 to 55/14 ].
- the phlegmatization of the metal powders of Ti, Zr and Hf and of alloy powders of these metals with Ni, Cr and Al occurs during and / or after reduction in the evacuable and gas tight retort by addition of a measured amount of hydrogen and / or nitrogen , Part of these gases can also be present in the retort from the very beginning.
- the passively acting gases can be introduced into the reaction vessel (the retort) after reaching the peak temperature during cooling of the reacted mass.
- Ni, Cr and Al have a dual function, they can not only serve for the production of alloys of Ti, Zr and Hf, but act in small amounts between 2000 ppm to 3% as phlegmatizing solid additives in the pure metals.
- non-metallic additives such as carbon, silicon, boron or metallic additives such as iron, nickel, chromium, aluminum and others can influence the reactivity of zirconium, titanium and hafnium to water, air and oxidants.
- Addition of silicon or boron generally slows down the burning rate only slightly, but can increase the ignition temperature.
- a rather negative example is iron, additions of iron lead to spray sparks, lower the ignition temperature of the zirconium metal rather and usually increase the ignitability to friction.
- Carbon can be introduced into the retort according to the invention by adding measured amounts of carbon dioxide or methane. It generally leads to a phlegmatization.
- the phlegmatization according to the invention of the metal powders of titanium, zirconium and hafnium or their alloy powder with gases can be realized on an industrial scale using a special reaction vessel (a retort).
- This reaction vessel according to the invention for the production of phlegmatized metal powder or alloy powder having an average particle size of less than 10 microns, consisting of or containing at least one of the reactive metals zirconium, titanium or hafnium, by metallothermal reduction of oxides or halides of said reactive metals by means of a Reduction metal according to the described method is characterized in that the reaction vessel consists of a usable in a heatable reduction oven retort crucible with a coolable lid and an inner crucible, wherein in the coolable lid at least one nozzle for introducing a passivating acting gas or solid is incorporated and to the Retortentiegel for attaching the retort cover a flange is welded to the underside of a
- the cooling is congruent under a ring on the flange extending seal and this cooling has no connection to the actual retort crucible.
- any other cooling media can be used as an alternative to water.
- organic heat transfer media such as heat transfer oils, preferably silicone oils, or even air can be used.
- a suitable silicone oil can be obtained, for example, as Therminol® VP from Solutia GmbH.
- the cooling media circulate in a common or in independent suitable cooling circuits.
- the lid may have the following connections: a nozzle with a heat-resistant, sealless ball valve or cock tap for releasing excess pressure, a nozzle for connecting a vacuum pump for evacuating the retort, a nozzle for introducing protective gas, such as argon, from a line, a Nozzle for introducing reactive gases, such as H 2 or N 2 , from a pipe, a nozzle for receiving a safety valve, a nozzle for connection to a vacuum and pressure gauge and a nozzle for passing one or several thermocouples (Pt / RhPt).
- a groove for receiving a sealing ring, preferably made of Viton, unless provided on the retort crucible, may be provided on the lid.
- the water cooling can be configured, for example, as running on the lid annular channel.
- the lid can preferably be connected via a screw with the flange.
- the cooling of the retort lid has no connection to the nozzle and passages of the cover plate.
- the cooling of the flange should have no connection to the retort crucible and the retort wall out.
- the wall thickness is at least 10 mm, preferably 15 mm.
- a flange 2 is welded with a material thickness of 30 mm and a ring width of 150 mm, on the underside of a cooling 3 is welded for cooling water.
- the flange 2 is preferably also made of the heat-resistant steel 1.4841 or a comparable steel.
- Decisive design feature is that the cooling 3 is exactly below a ring 4 extending on the flange 2 seal and this cooling 3 has no connection to the actual retort crucible 1.
- the flange 2 allows the attachment of the lid 5, wherein between the cover 5 and the flange 2 of the sealing ring 4 made of Viton, Perbunan, Teflon or other common sealing material is used, which allows the gas and vacuum-tight connection between the lid and retort crucible.
- the sealing ring 4 may optionally be inserted into a groove milled into the flange.
- a support ring with a spacer 20 is screwed to the crucible flange 2, which makes it possible to use the retort at different depths in the furnace chamber and the combustion chamber 18 of the heatable reduction furnace 17.
- the heating of the reduction furnace 17 may preferably be effected by means of an electric heating 16.1 or alternatively a gas heating 16.2.
- a spacer 20 with support ring is provided between the flange 2 and the heatable reduction furnace 17, a spacer 20 with support ring.
- the inner crucible 14 serves according to the Fig. 5 for receiving the batch mixture 15, that is, the mixture of the metal oxide and the reduction metal to be reduced.
- the inner crucible 14 is made of structural steel, heat-resistant steel or stainless steel, preferably St37 or VA, in a thickness of 2 depending on the purity requirements to 5 mm, preferably 2 to 4 mm.
- the reaction mass is kept away from the actual retort, which serves only as a "receptacle" during the duration of the reduction reaction.
- the inner crucible can be removed from the retort and optionally stored under protective gas in another vessel, eg a stainless steel drum, until the reduced mass contained in it is processed.
- a protective tube 21 can be inserted for receiving one or more thermocouples.
- a special feature is the execution of the cooling of the cover 5 and flange 2 of the reduction retort.
- Lid 5 and retort crucible 1 are gas-tight and vacuum-tight connected by a sealing ring 4 made of Viton, Perbunan, Teflon or other common sealing materials.
- the seals 4 may be designed as a flat ring or as an O-ring.
- the gaskets 4 must be cooled because they would be decomposed at the high reaction temperatures. The cooling takes place in this embodiment with water. It would be catastrophic if water entered the retort space through cracks or corrosion holes during the reduction reaction. This would lead to a violent evolution of hydrogen and an explosion of the retort.
- the design of the cooling is therefore a very important feature of the reaction vessel.
- the cooling 3 on the crucible flange is placed on the bottom of the flange 2 and has only one connection to the flange itself, but not to the retort wall. Thus, water can never penetrate into the retort from this area.
- the cover 5, the cooling is designed so that it cools only the surface of the lid 5, but has no connection to the nozzle and bushings. The cooling water would have to penetrate through the solid lid 5 to get into the retort, which is very unlikely with a wall thickness of at least 30 mm heat resistant steel.
- the cooling is as water cooling 6 in Fig. 3 shown in more detail.
- the retort crucible and retort lid are connected with a suitable number of screws and nuts 19.
- the retort lid 5 and retort crucible 1 existing retort can immediately after removal of the inner crucible 14 with the reacted and phlegmatized mass again to accommodate another Inner tiegel can be used with a new approach. Thus, several retorts can be reacted one after the other in an oven.
- An example of a metallothermal reduction using the above principles and the present invention is the recovery of zirconium in powder form by reduction of zirconium oxide with calcium for use in gettering (lamps, vacuum components) and military pyrotechnics, e.g. for the production of thermal batteries.
- Zirconia with a mean grain size of 5 +/- 0.5 micron measured by the Blaine method or the Fisher Sub Sieve Sizer method, is mixed with calcium chips or granules of 0.5 to 5 mm size.
- Calcium metal is added in the theoretically necessary stoichiometric amount.
- a small amount, for example 2 to 10% by weight, of the theoretically necessary stoichiometric amount of magnesium chips of similar size to calcium is additionally added.
- further additives for example carbon, silicon or silicon oxide and other substances can be added in order to influence the properties of the zirconium powder formed during the reduction.
- the amount of gaseous additives is measured to be in the range of 500 to about 5000 ppm in the later isolated zirconium powder, and "impurity" for solids of at least 2,000 to 3%.
- a small amount of silicon oxide is used, which reappears as Si contamination in the isolated zirconium powder.
- the mixture of the starting materials is carried out under argon in a Rhönradmischer, a helical mixer or other comparable mixing device for solids. All feedstocks must be kept scrupulously dry. Lowered by the addition of a small amount of the second reducing metal (magnesium) the threshold of the initial ignition, so that the reaction mixture is easier to ignite than when using calcium alone. Since magnesium vaporizes earlier than calcium, the vaporization of magnesium removes heat from the reaction mass, thereby limiting the peak temperature of the reacting mass.
- the starting materials are weighed in a drum mixer under Ar atmosphere, intimately mixed, transferred to an inner crucible and stored dry until used in the reduction of the invention under argon atmosphere.
- the inner crucible with the mixture of feedstocks in the retort crucible according to the invention is used, the retort closed by placing the lid, the entire retort pumped out twice to a final pressure of less than 1 mbar to remove the air and any moisture, and with argon flooded.
- a thermocouple is used to measure the temperature in the reaction space. It is connected to a pressure gauge, which displays both negative pressure to 0.1 mbar as overpressure to +1000 mbar.
- Compounds are made to gas pressure bottles with argon, nitrogen and hydrogen.
- the gas pressure bottles are equipped with fine pressure reducers, which are designed for a max. Print of 100 mbar are set.
- the pressure cylinders for nitrogen and hydrogen are filled with measured quantities of these gases.
- the protective gas argon must always be available in sufficient excess quantity.
- the reaction starts at a temperature of about. 100 - 140 ° C and 1100 ° C are reached within 2 minutes. After exceeding the peak temperature, recognizable by the falling of the measured temperature in the reaction space by means of a thermocouple, the necessary for phlegmatization or for adjusting the burning and ignition properties of the zirconium metal powder gas quantities are introduced.
- 50 liters of nitrogen and 130 liters of hydrogen from the connected compressed gas cylinders are added in the course of the cooling phase. This corresponds to an amount of 500 ppm of hydrogen and 2500 ppm of nitrogen in the resulting zirconium metal powder. The gases are rapidly absorbed by the zirconium metal during the cooling phase.
- the inner crucible with the reaction mass is removed from the retort, the reaction mass broken out, crushed with a jaw crusher and leached in hydrochloric acid.
- magnesium oxide and calcium oxide are converted to the corresponding chlorides and washed out.
- What remains is a metal slurry of fine zirconium metal powder, whose Grain size about that of the zirconium oxide used, ie 5 +/- 1 microns measured by Blaine or Fisher. The metal powder is washed out, wet sieved ( ⁇ 45 ⁇ m) and dried carefully ( ⁇ 80 ° C).
- the metal powder Due to the added auxiliaries (here SiO 2 ) and the gases, here N 2 and hydrogen, the metal powder can be safely processed in water and acid without reacting with water, and it can later be handled without spontaneous spontaneous combustion in air.
- the yield is 25-26 kg of a fine, gray zirconium metal powder.
- the burning rate of the metal powder thus obtained is measured as follows: into a steel block of 60 cm in length, 1 cm in height and 4 cm in width, a rectangular gutter, which is 2 mm deep and 3 mm wide, is continuously milled.
- the trough is filled with 15 g of the metal powder to be tested, the powder filling is ignited at one end and the time taken for the burning front to go through a marked distance of 500 mm distance is measured.
- the burning time is 80 +/- 10 seconds / 50 cm.
- the ignition temperature is 240 +/- 20 ° C.
- the electrical energy for ignition is about 18 ⁇ J.
- In the final product can be found due to a further hydrogen uptake in the aqueous workup, a total of 2000 ppm of hydrogen. Also impurities of the reduction metals are found in the metal powders, but these amounts i.a. low. The found amount of 1800 ppm silicon, 2500 ppm nitrogen and 1000 ppm titanium corresponds quite well to the theoretical amount.
- the retort is left in the reduction furnace after the reduction reaction with the reacted mass. Further heating from outside influences the grain size of the rare metal or its burning properties and chemical properties. By heating for several hours at about 900 ° C, a sintering effect can be achieved, which leads to a grain coarsening of the zirconium metal obtained. In the present example, by heating for 3-4 hours, the mean grain size of the zirconium metal can be increased from approximately 5 ⁇ m to 6 to 7 ⁇ m and the burning rate can be slowed from approximately 75 s / 50 cm to 100 to 120 s / 50 cm. The ignition point of the metal remains almost unchanged in this procedure and is at 250 ° C +/- 20 ° C.
- zirconium metal which is suitable for use in ignition systems of airbag detonators and militarily used ignition sets is proceeded as in Example (1), but the following starting materials are used: Zirconium oxide (average particle size 1.5 / -0.25 / + 0.5 ⁇ m) 36.0 kg Magnesium (chips, at least 99.8%, bulk density 0.45 g / cm 3 ) 17.1 kg silica 0.35 kg
- the burning rate in a gutter (compare Example (1) in air is 10 +/- 3 s / 50 cm.)
- the mean grain size of the metal powder is 1.7 +/- 0.3 ⁇ m
- Ignition point is 180 +/- 10 ° C.
- the minimum electrical ignition energy was measured at about 2 ⁇ J.
- the content of silicon corresponds approximately to the use and is 5900 ppm (theor. 6530 ppm).
- the hydrogen content in the final product is 1400 ppm (theor. 900 ppm), due to a further hydrogen uptake in the acid leaching.
- the nitrogen content in the final product is 4000 ppm (theoretical 5000 ppm).
- the high degree of ignitability of the metal powder results from the high degree of fineness and the high sensitivity to electrostatic charging. These metal powders are generally not dried, but stored and traded in suspension under at least 30% by weight of water.
- Example (1) The procedure is as in Example (1), but without additions of SiO 2 and TiO 2.
- Zirconium oxide (average particle size 4.5 ⁇ m) 36.0 kg
- Calcium granules 26.5 kg
- the reaction is carried out as in Example (1), but the retort is filled after pumping not with argon, but with 100 l of nitrogen (99,995). By heating, the reaction is started, it starts in this case already at 80 to 100 ° C and reaches a peak of about 1050 ° C.
- reaction mass After complete cooling, the reaction mass is broken, but not crushed leached, but finely ground under Argon atmosphere and exclusion of moisture to a particle size below 150 microns.
- calcium oxide and magnesium oxide as well as excess magnesium and calcium are added to 12 kg nickel powder (mean particle size after Fsss 5 microns) (attention, Ni powders are carcinogenic) and mixed under argon atmosphere in a drum mixer.
- the mass is then filled into the inner crucible, used in the retort according to the invention, evacuated and heated slowly under argon atmosphere, the oven temperature is limited to 860 ° C.
- the oven temperature is reached after about 1 h, the internal temperature measured in the reaction mixture begins to rise after about 3 to 5 h, then it runs within 15 minutes from about 400 ° C to 880-900 ° C. The heating will be switched off as soon as the implementation starts.
- the nickel oxide always contained in the nickel powder is reduced to Ni by the reducing agent excess still contained in the Zr reducing mass, and at the same time, the Zr powder combines with the nickel to form a Zr-Ni alloy having a composition of 70 % By weight of Zr and 30% by weight of nickel.
- 200 l of hydrogen are added.
- the reaction mass is allowed to cool overnight in the retort in a cooling rack under argon supply. After opening, the mass is broken up, crushed and leached in acid to wash out calcium and magnesium oxide. In this case, the leaching must be carried out in a strongly acetate-buffered hydrochloric acid, since the ZrNi alloy would be attacked by pure hydrochloric acid. The remaining as a suspension Zr / Ni alloy is wet sieved ( ⁇ 45 microns) and dried.
- the obtained Zr-Ni alloy powder has a grain size of 4-6 ⁇ m measured according to Blaine or Fisher.
- the yield is about 36 kg.
- the one burning time is 200 +/- 30 s / 50 cm measured in the hearth described in Example (1).
- the ignition point is 260-280 ° C, the hydrogen content at 0.2% (2000 ppm) versus 500 ppm theoretically.
- the nitrogen content was not determined, theoretically it is 1%. (10,000 ppm).
- As electrical minimum ignition energy was determined about 100 ⁇ J.
- the alloy powder is suitable for the production of delay igniters according to US specification MIL-Z-114108.
- the zirconium metal powder produced in the examples described are phlegmatized according to the invention and are not spontaneously self-ignitable, ie manageable upon access of air.
- the aqueous workup itself also contributes to the passivation of the metal surface.
- the latter also leads to the fact that Zr, Ti and Hf metal powders are surrounded by a thin oxide film and can thus be charged electrostatically. It can then enter a spontaneous inflammation, which is not based on the "classic" Dientzündige but is due to an electrostatic discharge.
- Zr, Ti and hafnium - metal powders must therefore always be handled in grounded, preferably metallic vessels and processed as far as possible under argon.
- appropriate safety measures must be taken and professional advice should be obtained from trained safety experts.
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Description
Die Erfindung betrifft die Herstellung passivierter, an der Luft handhabbarer feinster Metallpulver der Elemente Zirkonium, Titan und / oder Hafnium, mit einer mittleren Korngröße unter 10 µm (gemessen nach Permeabilitätsmethoden wie dem Blaine- oder Fisher-Verfahren) durch metallothermische Reduktion ihrer Oxide mittels Calcium und Magnesium.The invention relates to the production of passivated, air-manageable finest metal powder of the elements zirconium, titanium and / or hafnium, having a mean particle size below 10 microns (measured by permeability methods such as the Blaine or Fisher method) by metallothermal reduction of their oxides by means of calcium and magnesium.
Als phlegmatisierend wirkende Zusätze werden insbesondere Wasserstoff in einer Menge von mind. 500 ppm und Stickstoff in einer Menge von mindestens 1000 ppm verwendet, als phlegmatisierend wirkende feste Zusätze Kohlenstoff, Silizium, Bor, Nickel, Chrom und Aluminium in Mengen von mindestens 2000 ppm.In particular, hydrogen in an amount of at least 500 ppm and nitrogen in an amount of at least 1000 ppm are used as phlegmatizing additives, as phlegmatizing solid additives carbon, silicon, boron, nickel, chromium and aluminum in quantities of at least 2000 ppm.
Die Oxide können einzeln reduziert werden, um reine Metallpulver herzustellen. Sie können aber auch im Gemisch untereinander oder im Gemisch mit Metallpulvern und / oder Oxiden der Elemente Nickel, Chrom und Aluminium reduziert werden, um Legierungen von Titan, Zirkonium und Hafnium mit diesen Elementen herzustellen.The oxides can be individually reduced to produce pure metal powders. However, they may also be reduced in admixture with each other or in admixture with metal powders and / or oxides of the elements nickel, chromium and aluminum to produce alloys of titanium, zirconium and hafnium with these elements.
Metallothermische Reduktionen unter Verwendung von Calcium und Magnesium als Reduktionsmittel werden zur Gewinnung seltener Metalle aus ihren Oxiden dann eingesetzt, wenn diese auf andere Weise, z.B. elektrochemisch aus wässrigen Lösungen, aus geschmolzenen Salzen oder durch Reduktion ihrer Oxide mit Kohlenstoff oder mit Gasen wie Wasserstoff oder Kohlenmonoxid nicht oder nur in geringer Reinheit zu gewinnen sind. Ein typisches industrielles Beispiel dafür ist die Herstellung der Metalle der Seltenen Erden wie Yttrium, Cer, Lanthan und andere sowie des Metalls Beryllium aus ihren Oxiden oder Halogeniden mit Magnesium, Calcium oder Aluminium [Römpps Chemie-Lexikon "Metallothermie"]. Auβerdem setzt man die metallothermische Reduktion ein, um die seltenen Metalle in einer definierten fein - pulvrigen Form zu gewinnen, etwa für Anwendungen in der Pulvermetallurgie, der Pyrotechnik oder als Getter in der Vakuumtechnik. Dabei kann die Korngröße des zu erzielenden Metallpulvers durch die Wahl der Korngröße des entsprechenden zu reduzierenden Metalloxids weitgehend vorbestimmt werden [
Weiterhin beschreibt auch die
Durch Mischung verschiedener reduzierbarer Oxide kann man pulverförmige Legierungen herstellen, beispielsweise durch Mischen von Zirkoniumoxiod mit Titanoxid eine Legierung aus Zr und Ti oder von Zirkoniumoxid mit Nickel und Nickeloxid eine Legierung aus Zirkonium und Nickel. Durch Mischen der Reduktionsmetalle und geeignete Wahl der Korngrößen der Reduktionsmittel kann man den Start und die Kinetik des Reduktionsverlaufs beeinflussen. Die Wärmetönung der Reduktion richtet sich nach den zu reduzierenden Oxiden, dem Reduktionsmetall und möglichen Nebenreaktionen. Sie kann nach thermodynamischen Grundsätzen anhand der freien Reaktionsenthalpie der Edukte und der Produkte berechnet werden. Die stärkste Reduktionswirkung hat im Allgemeinen das Metall Calcium, gefolgt von Aluminium und Magnesium. Bei der Wahl des Reduktionsmittels ist zu beachten, dass dieses keine Legierung mit dem durch die Reduktion gewonnenen seltenen Metalls bilden sollte, es sei denn, dass dieses gerade gewollt wäre. Auch sollte das bei der Reduktion gebildete Metalloxid des Reduktionsmetalls mit dem zu reduzierenden Oxid keine Doppeloxide oder andere Mischoxide bilden, weil durch diese parallel laufende Nebenreaktion die Ausbeute vermindert wird. Da metallothermische Reduktionen meistens rasch und heftig mit hoher Wärmetönung ablaufen, ist der Dampfdruck des Reduktionsmetalls bei der zu erwartenden Reaktionstemperatur (meist 800 bis 1400°C) zu beachten und ggfls. zu berechnen. Darüber hinaus muss das bei der Reduktion gebildete Oxid des Reduktionsmetalls in Wasser oder wässrigen Säuren löslich sein, um es nach beendeter Umsetzung durch Laugung aus der Reaktionsmasse entfernen zu können. Die schlechte Löslichkeit der Oxide des Siliziums und Aluminiums sowie ihre Neigung zur Bildung von Mischoxiden ist der Grund dafür, dass diese an sich preisgünstigen Elemente als Reduktionsmittel häufig nicht eingesetzt werden.By mixing various reducible oxides, it is possible to produce pulverulent alloys, for example by mixing zirconium oxide with titanium oxide, an alloy of Zr and Ti or of zirconium oxide with nickel and nickel oxide an alloy of zirconium and nickel. By mixing the reducing metals and suitable choice of the particle sizes of the reducing agents, one can influence the start and the kinetics of the reduction process. The heat of the reduction depends on the oxides to be reduced, the reduction metal and possible side reactions. It can be calculated according to thermodynamic principles based on the free reaction enthalpy of the reactants and the products. The strongest reducing effect is generally metal calcium, followed by aluminum and magnesium. When choosing the reducing agent, it should be noted that this should not form an alloy with the rare metal obtained by the reduction, unless this is just wanted. Also, the metal oxide of the reduction metal formed with the reduction should not form double oxides or other mixed oxides with the oxide to be reduced, because the yield is reduced by this parallel side reaction. There Metallothermic reductions usually occur quickly and vigorously with high heat of reaction, the vapor pressure of the reducing metal at the expected reaction temperature (usually 800 to 1400 ° C) must be observed and if necessary. to calculate. In addition, the reduction metal oxide formed in the reduction must be soluble in water or aqueous acids in order to be able to remove it from the reaction mass by leaching after completion of the reaction. The poor solubility of the oxides of silicon and aluminum as well as their tendency to form mixed oxides is the reason that these low-priced elements are often not used as a reducing agent.
Metallothermische Reduktionsreaktionen sind im Allgemeinen selbstgängig. Man versteht darunter Reaktionen, die durch eine Initialzündung eingeleitet werden und danach ohne weitere Energiezufuhr von außen automatisch weiter laufen. Die Initialzündung kann chemisch, elektrisch (durch einen Glühdraht oder durch Induktion) oder einfach durch scharfes Erhitzen eines Teilbereichs des Metall / Metalloxid - Gemischs eingeleitet werden [
Als Reduktionsofen eignen sich gasbefeuerte Tiegelöfen oder elektrisch beheizte Öfen. Ansonsten spielt die Bauart des Reduktionsofens nur eine untergeordnete Rolle, theoretisch könnte die Reaktion auch durch ein Holz- oder Kohlefeuer unter der Retorte gestartet werden. Ein gasbeheizter Tiegelofen hat den Vorteil, dass die Retorte schnell erwärmt wird. Bei einer Temperatur von ca. 100 bis 450°C, abhängig von den Korngrößen und der Art der Einsatzstoffe, setzt eine Initialzündung ein, die an einem hot spot startet, der meist seitlich im unteren Drittel des Tiegels liegt, in dem sich die umzusetzende Mischung befindet. Bei der Reduktion der Oxide von Ti, Zr und Hf steigt die Temperatur danach innerhalb weniger Minuten auf Werte zwischen 900°C und 1200°C an, abhängig davon, ob Calcium oder Magnesium als primäres Reduktionsmetall eingesetzt wird. Calcium führt zu hohen über 1000°C liegenden, Magnesium zu etwas niedrigeren Spitzentemperaturen. Während des Aufheizens und besonders während der einsetzenden Reduktion steigt der Druck im Inneren der Retorte. Bei Erreichen eines Überdrucks von ca. 50 bis 100 mbar wird daher ein Ventil geöffnet und der Überdruck abgelassen, Es handelt sich meistens um Wasserstoff, der sich aus der Feuchtigkeit der Einsatzstoffe bildet, Magnesiummetalldampf sowie Alkalimetalldämpfe aus Verunreinigungen der Einsatzstoffe. Dabei kann es zu einer Flammenerscheinung am Ablassventil kommen. Entstehende Dämpfe und Stäube müssen am Ort ihrer Entstehung abgesaugt werden. Das Öffnen des Ventils kann manuell erfolgen, aber auch elektromechanisch oder pneumatisch, und es kann aus Sicherheitsgründen aus der Ferne z.B. unter Videobeobachtung gesteuert werden. Als Ablassventile für den Überdruck kommen in erster Linie dichtungslose Kükenhähne oder Kugelhähne mit großem Querschnitt zum Einsatz.As a reduction furnace gas-fired crucible furnaces or electrically heated furnaces are suitable. Otherwise, the design of the reduction furnace plays only a minor role, theoretically, the reaction could also be started by a wood or coal fire under the retort. A gas-fired crucible furnace has the advantage that the retort is heated quickly. At a temperature of about 100 to 450 ° C, depending on the grain sizes and the nature of the starting materials, sets an initial ignition, which starts at a hot spot, which is usually laterally in the lower third of the crucible in which the mixture to be reacted located. In the reduction of the oxides of Ti, Zr and Hf, the temperature then rises within a few minutes to values between 900 ° C and 1200 ° C, depending on whether calcium or magnesium is used as the primary reducing metal. Calcium leads to higher than 1000 ° C, magnesium to slightly lower peak temperatures. During heating, and especially during the onset of reduction, the pressure inside the retort increases. When reaching an overpressure of about 50 to 100 mbar, therefore, a valve is opened and the pressure released, It is usually hydrogen, resulting from the moisture of the starting materials forms, magnesium metal vapor and alkali metal vapors from impurities of the starting materials. This can lead to a flame on the drain valve. Resulting vapors and dusts must be extracted at the place of their formation. The opening of the valve can be done manually, but also electromechanical or pneumatic, and it can be controlled for security reasons remotely, for example, under video observation. As relief valves for the overpressure, primarily sealless plug valves or ball valves with a large cross section are used.
Metallothermische Reduktionen laufen - wenn sie gezündet wurden - unaufhaltsam weiter. Die einmal in Gang gesetzte Reaktion kann unter Anwendung üblicher Verfahrenstechniken wie Kühlen oder Zufügen von Verdünnungsmitteln nicht mehr gestoppt werden.Metal-thermal reductions continue to go on - when ignited - inexorably. Once initiated, the reaction can no longer be stopped using conventional processing techniques such as cooling or adding diluents.
Daraus ergibt sich, dass metallothermische Reduktionsreaktionen grundsätzlich besondere Sicherheitsvorkehrungen und wohlüberlegte Konstruktionen der Reaktionsgefäße erfordern:
- um die Reaktion kontrolliert in einer bestimmten Zeit und unter Schutzatmosphäre ablaufen zu lassen,
- um definiert kleine Mengen an Zusatzstoffen zur Beeinflussung der Materialeigenschaften der seltenen Metalle über die Gasphase während der Reaktion zufügen zu können,
- um die gesamte Reaktion derart unter Kontrolle zu halten, dass sie sich nicht explosionsartig entwickelt und
- um ein an der Luft handhabbares, nicht spontan selbstentzündliches Produkt zu erzeugen.
- in order to allow the reaction to take place in a controlled manner and in a controlled atmosphere,
- to be able to add small amounts of additives to influence the material properties of the rare metals via the gas phase during the reaction,
- to keep the entire reaction under control so that it does not explode and
- to produce an air-handleable, non-spontaneously auto-ignitable product.
Eine beinahe immer notwendige Maßnahme bei metallothermischen Reduktionen zur Gewinnung reaktiver seltener Metalle ist die Inertisierung der Reaktionsmasse vor, während und nach der Reduktionsreaktion. Dazu wird die Reduktionsreaktion unter einem inerten Schutzgas, meistens Argon oder Helium, ausgeführt. Alternativ kann die Reduktion auch im Vakuum gestartet und durchgeführt werden.An almost always necessary measure in metallothermal reductions to obtain reactive rare metals is the inertization of the reaction mass before, during and after the reduction reaction. For this purpose, the reduction reaction is carried out under an inert protective gas, usually argon or helium. Alternatively, the reduction can also be started and carried out in a vacuum.
Würde man die metallothermische Reduktion des Zirkoniums im Beispiel (1) etwa in einem Keramikbehälter an Luft oder unter einer Schlackendecke ähnlich wie in
Bei der Herstellung sehr reaktionsfreudiger seltener Metalle wie Zirkonium, Titan und Hafnium ist es notwendig, die Metallpulver gezielt zu phlegmatisieren, um sie später an Luft überhaupt handhaben und weiter verarbeiten zu können. Hochreines, völlig gasfreies und sauerstofffreies Titan, Zirkonium und Hafnium in feinster Pulverform sind pyrophor, d.h. sie würden sich bei Kontakt mit Luft augenblicklich entzünden und zu ihren Oxiden verbrennen. In der Literatur [
Hoch reines, entgastes Zirkonium kann sogar - wenn es in feinster Form vorliegt - unter Umständen mit Wasser reagieren, ähnlich der bekannten Reaktion von Alkalimetallen mit Wasser, wobei Wasserstoff gebildet und eine explosionsartige Umsetzung erfolgen würde. Über derartige Explosionsunfälle wird in der Literatur berichtet [
Metallisches Titan, Zirkonium und Hafnium sowie Legierungen dieser Metalle sind nur deshalb an Luft beständig, weil sie mit einer dichten, bei Raumtemperatur sauerstoffundurchlässigen Oxid- oder Oxinitrid-Hülle umgeben sind, der so bezeichneten Passivschicht. Die Passivierung ist auch von vielen anderen Metallen her bekannt, etwa von Aluminium, Zink und Chrom. Die Passivierung stellt sich bei den meisten Metallen von selbst ein. Durch Kontakt der Metalloberfläche mit dem Sauerstoff und Stickstoff der Luft, mit Feuchtigkeit und dem in Luft enthaltenen Kohlendioxid baut sich der schützende Passivfilm ohne besonderes Zutun auf. Dies ist nicht so bei den Metallen Ti, Zr und Hf sowie deren Legierungen, wenn sie in feiner Pulverform vorliegen und in einer schützenden Atmosphäre unter Argon, Helium oder im Vakuum erzeugt wurden. In diesem Fall muss durch gezielte Zugabe phlegmatisierender Stoffe, insbesondere der Gase Stickstoff und Wasserstoff, eventuell auch sauerstoffhaltiger Gase, dafür gesorgt werden, dass sich das Metallpulver bei Entnahme aus der Schutzgasatmosphäre nicht spontan entzündet oder sich - wie bereits erwähnt - bei Kontakt mit Wasser explosionsartig umsetzt.Metallic titanium, zirconium, and hafnium, and alloys of these metals, are only stable to air because they are surrounded by a dense, oxygen-impermeable, oxide or oxynitride envelope at room temperature, the so-called passive layer. The passivation is also known from many other metals, such as aluminum, zinc and chromium. Passivation occurs automatically on most metals. By contact of the metal surface with the oxygen and nitrogen of the air, with moisture and in air Carbon dioxide builds up the protective passive film without any special action. This is not so with the metals Ti, Zr and Hf and their alloys, when they are in fine powder form and produced in a protective atmosphere under argon, helium or in vacuum. In this case, it must be ensured by targeted addition of phlegmatizing substances, in particular the gases nitrogen and hydrogen, possibly also oxygen-containing gases, that the metal powder does not spontaneously ignite when removed from the inert gas atmosphere or - as already mentioned - when in contact with water explosive implements.
Die Aufgabe der vorliegenden Erfindung bestand nun darin, ein Verfahren und ein Reaktionsgefäß zur Durchführung dieses Verfahrens zur Herstellung von Metallpulvern oder Legierungspulvern der reaktionsfreudigen Metalle Zirkonium, Titan oder Hafnium aus den entsprechenden Oxiden bzw. Oxidmischungen bereitzustellen, wobei die hergestellten reaktionsfreudigen Metallpulver oder Legierungspulver anschließend, beispielsweise zum Zweck der Weiterverarbeitung, an der Luft handhabbar sein sollen.The object of the present invention was therefore to provide a method and a reaction vessel for carrying out this process for the production of metal powders or alloy powders of the reactive metals zirconium, titanium or hafnium from the corresponding oxides or oxide mixtures, wherein the prepared reactive metal powders or alloy powders subsequently, For example, for the purpose of further processing, to be handled in the air.
Die oben genannte Aufgabe wurde durch ein Verfahren zur Herstellung von Metallpulver oder Legierungspulver einer mittleren Korngröße unter 10 µm, bestehend aus oder enthaltend mindestens eines der reaktionsfreudigen Metalle Zirkonium, Titan oder Hafnium, durch metallothermische Reduktion von Oxiden oder Halogeniden der genannten reaktionsfreudigen Metalle mit Hilfe eines Reduktionsmetalls gelöst, wobei das Metallpulver oder Legierungspulver
- durch Zugabe eines passivierend wirkenden Gases oder Gasgemisches während und/oder nach der Reduktion der Oxide oder Halogenide phlegmatisiert wird und/oder
- durch Zugabe eines passivierend wirkenden Feststoffs vor der Reduktion der Oxide oder Halogenide phlegmatisiert wird,
- is phlegmatized by adding a passivating gas or gas mixture during and / or after the reduction of the oxides or halides and / or
- by the addition of a passivating solid prior to the reduction of the oxides or halides is phlegmatized,
Das erfindungsgemäße Verfahren erlaubet einerseits die Durchführung der Reduktionsreaktion unter Schutzgasen wie Argon oder Helium oder im Vakuum, um unkontrollierten Zutritt von Luft und Feuchtigkeit auszuschließen. Die Konstruktion des Reaktionsgefäßes erlaubt weiterhin insbesondere die gezielte Zugabe einer abgemessenen Menge von Gasen während und/oder nach der Reduktionsreaktion, um die gebildeten Metalle oder Legierungen gezielt zu phlegmatisieren und in ihrem chemischen Verhalten zu beeinflussen. Die Konstruktion erlaubt ferner die Reduktion der Oxide oder Oxidmischungen unter einer reaktiven Gasatmosphäre, insbesondere unter Wasserstoff, wenn beabsichtigt wird, Hydride der Metalle Ti, Zr und Hf herzustellen. Sie erlaubt auch die Hydrierung schmelzmetallurgisch hergestellter Legierungen, z.B. einer Legierung aus 70 % Zr und 30 % Nickel oder von Titanschwamm durch Erhitzen und Einleiten von Wasserstoff. Neben Wasserstoff können auch Ammoniak, Methan, Kohlenmonoxid, Kohlendioxid und Stickstoff in die Retorte eingeleitet werden, um Hydride, Subhydride, Carbide, Nitride, Hydrid-Nitrid-Gemische oder Oxinitride der Metalle Zirkonium, Titan und Hafnium herzustellen. Die Konstruktion beinhaltet eine spezielle Ausführung der Kühlung von Flansch und Deckel, um das ungewollte Eindringen von Kühlwasser in den Retortenraum zu verhindern. Eine spezielle Abstandshalterung mit Stützring gestattet es, die Retorte in unterschiedliche Tiefen in den Brennraum des Reduktionsofens einzusetzen.On the one hand, the process according to the invention allows the reduction reaction to be carried out under protective gases, such as argon or helium, or in vacuo, in order to prevent uncontrolled access of air and moisture. The construction of the reaction vessel further allows in particular the targeted addition of a measured amount of gases during and / or after the reduction reaction in order to specifically phlegmatize the metals or alloys formed and to influence their chemical behavior. The construction further permits the reduction of the oxides or oxide mixtures under a reactive gas atmosphere, especially under hydrogen, when it is intended to produce hydrides of the metals Ti, Zr and Hf. It also allows the hydrogenation of alloys made by fusion metallurgy, e.g. an alloy of 70% Zr and 30% nickel or titanium sponge by heating and introducing hydrogen. In addition to hydrogen, ammonia, methane, carbon monoxide, carbon dioxide and nitrogen may also be introduced into the retort to produce hydrides, subhydrides, carbides, nitrides, hydride-nitride mixtures or oxynitrides of the metals zirconium, titanium and hafnium. The design incorporates a special flange and lid cooling design to prevent unwanted ingress of cooling water into the retort space. A special spacer with support ring allows the retort to be inserted at different depths into the combustion chamber of the reduction furnace.
Das dabei eingesetzte Reduktionsmetall ist vorzugsweise Calcium und/oder Magnesium. Calcium und Magnesium können also einzeln oder auch gemeinsam verwendet werden. Grundsätzlich können weitere Zusätze, wie Kohlenstoff, Silizium oder Siliziumoxid und andere Stoffe, zugefügt werden, um die Eigenschaften des bei der Reduktion entstehenden reaktionsfreudigen Metallpulvers zu beeinflussenThe reduction metal used is preferably calcium and / or magnesium. Calcium and magnesium can therefore be used individually or together. In principle, further additives, such as carbon, silicon or silicon oxide and other substances, can be added in order to influence the properties of the reactive metal powder produced during the reduction
Als passivierend wirkendes Gas wird vorzugsweise Stickstoff und/oder Wasserstoff eingebracht. Dabei sollten mindestens 500 ppm Wasserstoff und 1000 ppm Stickstoff in den Metallpulvern enthalten sein, um die oben geschilderten Reaktionen zu vermeiden. Aus Sicherheitsgründen sollte die Menge an Wasserstoff besser mindestens 1000 ppm (0,1 %), vorzugsweise 1000 bis 2000 ppm, und an Stickstoff mindestens 2000 ppm (0,2 %), vorzugsweise 2000 - 3000 ppm, betragen. Stickstoff und Wasserstoff können auch in der Form von Ammoniak eingebracht werden.As a passivating gas preferably nitrogen and / or hydrogen is introduced. At least 500 ppm of hydrogen and 1000 ppm of nitrogen should be present in the metal powders in order to avoid the above-mentioned reactions. For safety reasons, the amount of hydrogen should be better at least 1000 ppm (0.1%), preferably 1000 to 2000 ppm, and nitrogen at least 2000 ppm (0.2%), preferably 2000 - 3000 ppm. Nitrogen and hydrogen can also be introduced in the form of ammonia.
Als passivierend wirkende Feststoffe können mindestens 2000 ppm (0,2 Gew.%) und höchstens 30000 ppm (3 Gew.%) Kohlenstoff, Silizium, Bor, Nickel, Chrom und/oder Aluminium eingebracht werden. Der passivierend wirkende Feststoff kann auch in Form eines feinen Oxids der Elemente Ni, Cr, Al, Si und B mit einer mittleren Korngröße unter 20 µm eingebracht und mit dem Metalloxid gemeinsam reduziert werden. Alternativ ist auch das Einbringen des passivierend wirkenden Feststoffs in Form eines feinen Pulvers der Elemente Ni, Cr, Al, Si, B oder C mit einer mittleren Korngröße unter 20 µm möglich. Gemäß einer weiteren Ausführungsvariante des Verfahens kann Kohlenstoff über die Gasphase in Form von Methan, Kohlendioxid oder Kohlenmonoxid eingebracht werden. Schließlich können die passivierend wirkenden Gase und Feststoffe auch gemeinsam eingebracht werden.At least 2,000 ppm (0.2% by weight) and at most 30,000 ppm (3% by weight) of carbon, silicon, boron, nickel, chromium and / or aluminum can be introduced as passivating solids. The passivating solid can also be introduced in the form of a fine oxide of the elements Ni, Cr, Al, Si and B having an average particle size of less than 20 μm and reduced together with the metal oxide. Alternatively, it is also possible to introduce the passivating solid in the form of a fine powder of the elements Ni, Cr, Al, Si, B or C with an average particle size of less than 20 μm. According to a further embodiment variant of the method, carbon can be introduced via the gas phase in the form of methane, carbon dioxide or carbon monoxide. Finally, the passivating gases and solids can also be introduced together.
Die Zündwilligkeit der phlegmatisierte Metallpulver oder Legierungspulver kann durch Auswaschen submikroskopisch kleiner Teilchen von weniger als 0,2 µm Korngröße während des Laugens und/oder Waschens weiter verringert werden.The ignitability of the phlegmatized metal powders or alloy powders can be further reduced by washing out submicroscopic particles of less than 0.2 μm grain size during leaching and / or washing.
Der Mechanismus bzw. der Grund dieser Phlegmatisierung ist nicht genau bekannt. Man kann vermuten, aber nicht unbedingt davon ausgehen, dass diese geringen Gasmengen zu einer "Schichtbildung" von Metallhydrid oder Metallnitrid auf der Partikeloberfläche führen. Bei einer eventuellen Porosität, verbunden mit einer hohen spez. Oberfläche des Metallpulvers, sind dann gewisse Mindestmengen an N und H erforderlich, um eine mindestens monomolekulare Bedeckung der Metalloberfläche sicher zu stellen. Andererseits besitzen die Metalle Ti, Zr und Hf eine beträchtliche Löslichkeit für Gase. Im Zirkonium-Metallgitter können sich beispielsweise 5 Atom% Wasserstoff und bis zu 20 Atom% Stickstoff in fester Lösung befinden [
Eine hypothetische Vorstellung des Erfinders ist folgende: durch die Einlagerung der Gase in das Metallgitter wird das gesamte Energieniveau der freien Elektronen im Metall soweit abgesenkt, dass die spontane Umsetzung mit Sauerstoff unter Verbrennung oder die Reaktion mit Wasser unterbleibt. Bei der folgenden nasschemischen Aufbereitung der Metallpulver in Wasser und Säure bildet sich erst die eigentliche, oxidische Passivschicht auf der Partikeloberfläche durch eine langsame Oxidationsreaktion mit Luftsauerstoff bzw. durch langsame Reaktion mit Wasser. Da das Metallpulver bei der nasschemischen Aufarbeitung auf Raumtemperatur oder höchstens auf Siedetemperatur des Wassers erwärmt wird, sind alle Diffusionsvorgänge langsam und es kann sich in der Tat jetzt eine dichte, fest haftende "Passivschicht" aus Metalloxid (und Metallnitrid) ausbilden, die das Metall dauerhaft vor der weiteren Oxidation schützt. Diese Hypothese wird durch hier nicht näher erläuterte Versuche des Erfinders gestützt, in denen bei der Aufbereitung schwach oxidierende Stoffe wie Wasserstoffperoxid, Hypochlorit, Alkalinitrit oder schichtbildende Stoffe wie Phosphorsäure, Phosphate und Chromate zugesetzt wurden, welche die Passivierung der Metallpulver erhöhten. Gestützt wird diese Hypothese auch dadurch, dass man in der Praxis während der Aufbereitung der Metallpulver in Säuren und später im Waschwasser stets eine schwache Gasentwicklung (Wasserstoff) in Form feinster Gasbläschen beobachten kann, die nach einer Zeit von 3 bis 12 h beendet ist. Auch muss man feststellen, dass die in den Metallpulvern analysierten Gehalte von Wasserstoff stets höher sind als die aufgrund der Wasserstoffzugabe theoretisch ermittelten Werte. Die Metalle nehmen also auch während der nasschemischen Aufbereitung nochmals Wasserstoff auf, dessen Ursprung in der Zersetzung überschüssigen Reduktionsmittels (Mg, Ca) aber auch in einer an der Oberfläche stattfindenden Reaktion zwischen dem Metall und Wasser liegt.A hypothetical idea of the inventor is the following: by the inclusion of the gases in the metal grid, the total energy level of the free electrons in the metal is lowered so far that the spontaneous reaction with oxygen under combustion or the reaction with water is omitted. In the following wet-chemical preparation of the metal powders in water and acid, only the actual, oxidic passive layer on the particle surface is formed by a slow oxidation reaction with atmospheric oxygen or by slow reaction with water. Since the metal powder is heated to room temperature or at most to the boiling point of the water in the wet-chemical processing, all diffusion processes are slow and it can now form a dense, firmly adhering "passive layer" of metal oxide (and metal nitride), the metal permanently protects against further oxidation. This hypothesis is supported by experiments of the inventor, which are not described here, in which weakly oxidizing substances such as hydrogen peroxide, hypochlorite, alkali nitrite or layer-forming substances such as phosphoric acid, phosphates and chromates were added during the preparation, which increased the passivation of the metal powders. This hypothesis is also supported by the fact that in practice during the preparation of the metal powders in acids and later in the wash water, a weak evolution of gas (hydrogen) in the form of very fine gas bubbles can always be observed, which is completed after a time of 3 to 12 hours. It must also be noted that the contents of hydrogen analyzed in the metal powders are always higher than the values theoretically determined on the basis of hydrogen addition. The metals therefore also take up hydrogen again during the wet-chemical preparation, the origin of which lies in the decomposition of excess reducing agent (Mg, Ca) but also in a superficial reaction between the metal and water.
Erfindungsgemäß soll insbesondere der Effekt der Einlagerung von Gasen in das Metallgitter ausgenutzt werden. Eine solche Einlagerung wird vorteilhafterweise gerade dadurch erreicht, dass die phlegmatisierenden Verbindungen insbesondere bereits während der Reduktionsreaktion hinzugefügt werden.According to the invention, in particular the effect of the incorporation of gases into the metal grid is to be exploited. Such incorporation is advantageously achieved precisely in that the phlegmatizing compounds are added in particular already during the reduction reaction.
Der Grad der Passivierung ist schwer zu quantifizieren, er kann am besten noch aus dem Zündpunkt der Metallpulver an Luft abgeleitet werden. Zur Messung des Zündpunktes fester Stoffe stehen verschiedene, z.T. auch genormte Methoden zur Verfügung. Für die Metalle Ti, Zr und Hf eignet sich folgende einfache Versuchsanordnung: in einen Kupfer- oder Stahlzylinder mit einem Durchmesser und einer Höhe von jeweils 70 mm wird mittig ein Loch von 15 mm Durchmesser und 35 mm Tiefe gebohrt. Im Abstand von 4 mm wird ein 5 mm dickes Loch von ebenfalls 35 mm Tiefe gebohrt, das zur Aufnahme eines Thermoelements dient. Der Block wird auf ca. 140 - 150°C gleichmäßig vorgewärmt, dann wird eine Menge von 1 - 2 g des zu prüfenden Metallpulvers in die größere Bohrung eingefüllt und es wird weiter erhitzt, bis zur Zündung. Diese kann optisch (z.B. mittels Videokamera) erkannt werden. Durch Auswertung der Zeit / Temperatur - Kurve des Thermoelements kann man den Zündpunkt recht genau bestimmen. Liegen die Zündpunkte unter 150°C kann man nicht von einer sicheren Passivierung oder Phlegmatisierung ausgehen. Metallpulver mit solch niedrigen Zündpunkten sollten durch Verbrennung an einem sicheren Ort vernichtet werden.The degree of passivation is difficult to quantify, it can best be deduced from the ignition point of the metal powder in air. To measure the ignition point of solid substances are different, z.T. also standardized methods available. For the metals Ti, Zr and Hf, the following simple test arrangement is suitable: in a copper or steel cylinder with a diameter and a height of 70 mm each, a hole of 15 mm diameter and 35 mm depth is drilled in the middle. At a distance of 4 mm, a
Auch die Brennzeit gibt Hinweise auf den Grad der Phlegmatisierung Die Methode ist in Beispiel 1 beschrieben. Hinweise darauf sind auch aus Messungen der elektrischen Mindestzündenergie zu entnehmen, die jedoch sehr schwierig zu ermitteln ist. [
In der vorliegenden Erfindung erfolgt die Phlegmatisierung der Metallpulver von Ti, Zr und Hf sowie von Legierungspulvern dieser Metalle mit Ni, Cr und Al während und/oder nach der Reduktion in der evakuierbaren und gasdichten Retorte durch Zugabe einer abgemessenen Menge an Wasserstoff und / oder Stickstoff. Ein Teil dieser Gase kann auch bereits von Anfang an in der Retorte vorhanden sein. Besser und genauer können die passivierend wirkenden Gase nach dem Erreichen der Spitzentemperatur beim Abkühlen der ausreagierten Masse in das Reaktionsgefäß (die Retorte) eingeleitet werden.In the present invention, the phlegmatization of the metal powders of Ti, Zr and Hf and of alloy powders of these metals with Ni, Cr and Al occurs during and / or after reduction in the evacuable and gas tight retort by addition of a measured amount of hydrogen and / or nitrogen , Part of these gases can also be present in the retort from the very beginning. The passively acting gases can be introduced into the reaction vessel (the retort) after reaching the peak temperature during cooling of the reacted mass.
Die Elemente Ni, Cr und Al haben eine doppelte Funktion, sie können nicht nur zur Herstellung von Legierungen des Ti, Zr und Hf dienen, sondern wirken in kleinen Mengen zwischen 2000 ppm bis zu 3 % auch als phlegmatisierende feste Zusätze in den reinen Metallen.The elements Ni, Cr and Al have a dual function, they can not only serve for the production of alloys of Ti, Zr and Hf, but act in small amounts between 2000 ppm to 3% as phlegmatizing solid additives in the pure metals.
Daneben vermögen nichtmetallische Zusätze wie Kohlenstoff, Silizium, Bor oder metallische Zusätze wie Eisen, Nickel, Chrom, Aluminium und andere die Reaktionsfreudigkeit des Zirkoniums, Titans und Hafniums gegenüber Wasser, Luft und Oxidationsmitteln zu beeinflussen. Ein Zusatz von Silizium oder Bor verlangsamt im Allgemeinen die Brenngeschwindigkeit nur wenig, kann aber die Zündtemperatur heraufsetzen. Ein eher negatives Beispiel ist Eisen, Zusätze von Eisen führen zu Sprühfunken, setzen die Zündtemperatur des Zirkoniummetalls eher herab und erhöhen meist die Zündwilligkeit gegenüber Reibung. Kohlenstoff kann in der erfindungsgemäßen Retorte durch Zugabe abgemessener Mengen Kohlenstoffdioxid oder Methan eingeführt werden. Er führt im Allgemeinen zu einer Phlegmatisierung. Andere Elemente setzt man besser in Form ihrer Oxide oder direkt als Pulver in elementarer Form dem Ansatz zu. Der Zusatz fester Stoffe in geringer Menge ist allerdings mit dem Problem verbunden, dass aufgrund ungenügender Vermischung oder durch Entmischung nicht alle Metallpartikel mit dem Zusatz in Kontakt kommen, so dass neben dotierten, phlegmatisierten Metallpartikeln auch solche existieren, die nicht mit dem Zusatz legiert wurden. Letztere können sich bei der Aufbereitung entzünden und zur Verbrennung des gesamten Ansatzes führen. Gasförmige Zusätze verteilen sich demgegenüber gleichmäßig im gesamten Retortenraum und erreichen im Allgemeinen alle gebildeten Metallpartikel. Es ist daher empfehlenswert, in erster Linie mit gasförmigen Zusätzen zu arbeiten.In addition, non-metallic additives such as carbon, silicon, boron or metallic additives such as iron, nickel, chromium, aluminum and others can influence the reactivity of zirconium, titanium and hafnium to water, air and oxidants. Addition of silicon or boron generally slows down the burning rate only slightly, but can increase the ignition temperature. A rather negative example is iron, additions of iron lead to spray sparks, lower the ignition temperature of the zirconium metal rather and usually increase the ignitability to friction. Carbon can be introduced into the retort according to the invention by adding measured amounts of carbon dioxide or methane. It generally leads to a phlegmatization. Other elements are better put in the form of their oxides or directly as a powder in elemental form the approach to. However, the addition of solids in a small amount is associated with the problem that due to insufficient mixing or demixing not all metal particles come into contact with the additive, so that in addition to doped, phlegmatized metal particles also exist that were not alloyed with the additive. The latter can ignite in the treatment and lead to the combustion of the entire approach. In contrast, gaseous additives are uniformly distributed throughout the entire retort space and generally reach all the metal particles formed. It is therefore recommended to work primarily with gaseous additives.
Die erfindungsgemäße Phlegmatisierung der Metallpulver von Titan, Zirkonium und Hafnium oder deren Legierungspulver mit Gasen kann im industriellen Maßstab unter Einsatz eines speziellen Reaktionsgefäßes (einer Retorte) verwirklicht werden. Dieses erfindungsgemäße Reaktionsgefäß zur Herstellung von phlegmatisiertem Metallpulver oder Legierungspulver einer mittleren Korngröße unter 10 µm, bestehend aus oder enthaltend mindestens eines der reaktionsfreudigen Metalle Zirkonium, Titan oder Hafnium, durch metallothermische Reduktion von Oxiden oder Halogeniden der genannten reaktionsfreudigen Metalle mit Hilfe eines Reduktionsmetalls nach dem beschriebenen Verfahrens ist dadurch gekennzeichnet, dass das Reaktionsgefäß aus einem in einen beheizbaren Reduktionsofen einsetzbaren Retortentiegel mit einem kühlbaren Deckel und einem Innentiegel besteht, wobei in den kühlbaren Deckel mindestens ein Stutzen zum Einleiten eines passivierend wirkenden Gases oder Feststoffs eingearbeitet ist und an den Retortentiegel zum Aufsetzen des Retortendeckels ein Flansch angeschweißt ist auf den unterseitig eine Kühlung für ein Kühlmedium aufgeschweißt ist. Anstelle der genannten Schweißverbindungen sind auch andere geeignete Verbindungsarten im Sinne dieser Erfindung.The phlegmatization according to the invention of the metal powders of titanium, zirconium and hafnium or their alloy powder with gases can be realized on an industrial scale using a special reaction vessel (a retort). This reaction vessel according to the invention for the production of phlegmatized metal powder or alloy powder having an average particle size of less than 10 microns, consisting of or containing at least one of the reactive metals zirconium, titanium or hafnium, by metallothermal reduction of oxides or halides of said reactive metals by means of a Reduction metal according to the described method is characterized in that the reaction vessel consists of a usable in a heatable reduction oven retort crucible with a coolable lid and an inner crucible, wherein in the coolable lid at least one nozzle for introducing a passivating acting gas or solid is incorporated and to the Retortentiegel for attaching the retort cover a flange is welded to the underside of a cooling for a cooling medium is welded. Instead of the aforementioned welded joints are also other suitable types of connection in the context of this invention.
In der Literatur wird bei der Beschreibung metallothermischer Reduktionsreaktionen meistens nur erwähnt, dass die Reaktion in einer geschlossenen stählernen Retorte unter Schutzgas ausgeführt wird, ohne auf konstruktive Merkmale solcher Retorten einzugehen. Oft werden fest verschraubte Stahlretorten erwähnt, sogenannte Bombenrohre, die keine Öffnungen besitzen, allenfalls einen Anschluß für ein Manometer. Derartige Konstruktionen erlauben zwar die Zugabe von inerten Gasen (Ar, He), reaktiven Gasen (H2, CO, CO2, NH3, CH4) oder festen Zusätzen (Ni, NiO, Cr, Cr203, C, Si, SiO2, B, B2O3) vor der Umsetzung in dem Maß, wie es der freie Retortenraum gestattet, nicht aber während und nach der Reduktion. Derartige Retorten sind für die wissenschaftliche Ermittlung der Eigenschaften seltener Metalle durchaus geeignet, nicht aber, um in kurzer Zeit große Mengen der seltenen Metalle herzustellen. Mit fest verschlossenen Reaktionsgefäßen können die in der Pyrotechnik und Gettertechnik wichtigen Eigenschaften wie Brenngeschwindigkeit, Zündpunkt und der Grad der Phlegmatisierung nicht gezielt eingestellt werden. Auch ist das Öffnen fest verschlossener Stahlretorten nach erfolgter Umsetzung eine nicht ungefährliche Angelegenheit, da oft keine Information über den herrschenden Druck besteht. Nicht gekühlte verschraubte Retorten erfordern zwischen dem Deckel und dem Retortentiegel eine hitzefeste metallische oder keramische Dichtung (Kupfer, Silber oder hitzefeste Fasern), die in den meisten Fällen nur einmal verwendet werden kann. Auch können große Retorten auf diese Weise nur schlecht gedichtet werden, solche Dichtungen erlauben nur das Verwenden kleiner Retorten im kg - Maßstab oder darunter.In the literature, the description of metallo-thermal reduction reactions usually only mentions that the reaction is carried out in a closed steel retort under protective gas, without going into constructive features of such retorts. Often firmly screwed steel retorts are mentioned, so-called bomb tubes, which have no openings, possibly a connection for a manometer. Although such constructions allow the addition of inert gases (Ar, He), reactive gases (H 2 , CO, CO 2 , NH 3 , CH 4 ) or solid additives (Ni, NiO, Cr, Cr 2 0 3 , C, Si , SiO 2 , B, B 2 O 3 ) before the reaction to the extent permitted by the free retort space, but not during and after the reduction. Such retorts are quite suitable for the scientific determination of the properties of rare metals, but not to produce large quantities of the rare metals in a short time. With tightly closed reaction vessels, the important properties in pyrotechnics and getter technology, such as burning speed, ignition point and the degree of phlegmatization, can not be specifically adjusted. Also, the opening of tightly closed steel retorts after the implementation of a non-dangerous matter, since there is often no information about the prevailing pressure. Uncooled screw-retained retorts require a heat-resistant metallic or ceramic seal (copper, silver, or heat-resistant fibers) between the lid and the retort cup, which in most cases can only be used once. Also, large retorts are poorly sealed in this way, such seals only allow the use of small retorts on a kg scale or below.
Gemäß einer vorteilhaften Ausführung des Reaktionsgefäßes liegt die Kühlung deckungsgleich unter einer auf dem Flansch ringförmig verlaufenden Dichtung und diese Kühlung hat keine Verbindung zum eigentlichen Retortentiegel.According to an advantageous embodiment of the reaction vessel, the cooling is congruent under a ring on the flange extending seal and this cooling has no connection to the actual retort crucible.
Für die Kühlung am Tiegelflansch bzw. zur Kühlung des Deckels können als Alternative zu Wasser auch beliebige weitere Kühlmedien genutzt werden. So können beispielsweise organische Wärmeübertragungsmedien, wie Wärmeträgeröle, vorzugsweise Silikonöle, oder auch Luft verwendet werden. Ein geeignetes Silikonöl kann beispielsweise als Therminol® VP von der Firma Solutia GmbH bezogen werden. Die Kühlmedien zirkulieren in einem gemeinsamen oder in unabhängigen geeigneten Kühlkreisläufen.For cooling on the crucible flange or for cooling the lid, any other cooling media can be used as an alternative to water. For example, organic heat transfer media, such as heat transfer oils, preferably silicone oils, or even air can be used. A suitable silicone oil can be obtained, for example, as Therminol® VP from Solutia GmbH. The cooling media circulate in a common or in independent suitable cooling circuits.
In den kühlbaren Deckel ist neben dem Stutzen zum Einleiten eines passivierend wirkenden Gases oder Feststoffs mindestens ein weiterer Stutzen für den Anschluss einer Vakuumpumpe eingearbeitet. Weiterhin kann der Deckel folgende Anschlüsse besitzen: einen Stutzen mit einem hitzefesten, dichtungslosen Kugelhahn oder Kükenhahn zum Ablassen von Überdruck, einen Stutzen für den Anschluss einer Vakuumpumpe zum Evakuieren der Retorte, einen Stutzen zum Einleiten von Schutzgas, wie Argon, aus einer Leitung, einen Stutzen zum Einleiten reaktiver Gase, wie H2 oder N2, aus einer Leitung, einen Stutzen zur Aufnahme eines Sicherheitsventils, einen Stutzen zum Anschluss an ein Vakuum- und Druckmessgerät und einen Stutzen zum Durchführen eines oder mehrerer Thermoelemente (Pt / RhPt). Gegebenenfalls kann am Deckel weiterhin eine Rille zur Aufnahme eines Dichtungsrings, vorzugsweise aus Viton, sofern nicht am Retortentiegel vorhanden, vorgesehen sein. Die Wasserkühlung kann beispielweise als auf dem Deckel verlaufender Ringkanal ausgestaltet sein. Der Deckel kann vorzugsweise über eine Verschraubung mit dem Flansch verbunden werden.In the coolable lid, at least one additional nozzle for the connection of a vacuum pump is incorporated in addition to the nozzle for introducing a passively acting gas or solid. Furthermore, the lid may have the following connections: a nozzle with a heat-resistant, sealless ball valve or cock tap for releasing excess pressure, a nozzle for connecting a vacuum pump for evacuating the retort, a nozzle for introducing protective gas, such as argon, from a line, a Nozzle for introducing reactive gases, such as H 2 or N 2 , from a pipe, a nozzle for receiving a safety valve, a nozzle for connection to a vacuum and pressure gauge and a nozzle for passing one or several thermocouples (Pt / RhPt). Optionally, a groove for receiving a sealing ring, preferably made of Viton, unless provided on the retort crucible, may be provided on the lid. The water cooling can be configured, for example, as running on the lid annular channel. The lid can preferably be connected via a screw with the flange.
Von besonderer Bedeutung ist weiterhin, dass die Kühlung des Retortendeckels keine Verbindung zu den Stutzen und Durchführungen der Deckelplatte aufweist. Dabei sollte insbesondere die Kühlung des Flansches keine Verbindung zum Retortentiegel und der Retortenwand hin aufweisen.Of particular importance is further that the cooling of the retort lid has no connection to the nozzle and passages of the cover plate. In particular, the cooling of the flange should have no connection to the retort crucible and the retort wall out.
Weitere Vorteile und Einzelheiten des erfindungsgemäßen Verfahrens sowie des Reaktionsgefäßes zur Durchführung metallothermischer Reduktionen zur Gewinnung der Metalle Zirkonium, Titan, Hafnium und ihrer Legierungen sowie anderer seltener Metalle in fein - pulvriger, phlegmatisierter Form ergeben sich aus der nachfolgenden nicht einschränkenden Darstellung im Zusammenhang mit den Zeichnungen. Dabei zeigen:
- Fig. 1
- einen Reduktionsofen mit einem Reaktionsgefäß zur Durchführung metallothermischer Reduktionen zur Gewinnung der Metalle Zirkonium, Titan, Hafnium und ihrer Legierungen sowie anderer seltener Metalle,
- Fig. 2
- einen Retortentiegel,
- Fig. 3
- einen gekühlten Retortendeckel,
- Fig. 4
- eine Distanzhalterung und
- Fig. 5
- einen Innentiegel.
- Fig. 1
- a reduction furnace with a reaction vessel for carrying out metal-thermal reductions to obtain the metals zirconium, titanium, hafnium and their alloys and other rare metals,
- Fig. 2
- a retort pot,
- Fig. 3
- a cooled retort lid,
- Fig. 4
- a distance bracket and
- Fig. 5
- an inner crucible.
Der Retortentiegel 1 besteht gemäß den
Der kühlbare Deckel besteht gemäß der
einem Deckel 5 aus mindestens 25 mm, vorzugsweise 30 mm, dickem hitzefestem Stahl, 1.4841 oder einem vergleichbaren Material,einem Stutzen 12 mit einem hitzefesten, dichtungslosen Kugelhahn oder Kükenhahn zum Ablassen von Überdruck,einem Stutzen 13 für den Anschluss einer Vakuumpumpe zum Evakuieren der Retorte,einem Stutzen 7 zum Einleiten von Schutzgas, wie Argon, aus einer Leitung,einem Stutzen 8 zum Einleiten reaktiver Gase, wie H2 oder N2, aus einer Leitung,- einem Stutzen 9 zur Aufnahme eines Sicherheitsventils (p = 0,25 bar),
einem Stutzen 11 zum Anschluss an ein Vakuum- und Druckmessgerät, (eines Monometers, 0,1 - 1500 mbar),einem Stutzen 10 zum Durchführen eines oder mehrerer Thermoelemente (Pt / RhPt),der Wasserkühlung 6 und- gegebenenfalls einer Rille zur Aufnahme eines Dichtungsrings, vorzugsweise aus Viton, sofern nicht am Retortentiegel vorhanden.
Die Wasserkühlung 6 kann beispielweise als aufdem Deckel 5 verlaufender Ringkanal ausgestaltet sein.Der Deckel 5 kann vorzugsweise über eine Verschraubung 19mit dem Flansch 2 verbunden werden.
- a
cover 5 of at least 25 mm, preferably 30 mm, thick heat-resistant steel, 1.4841 or a comparable material, - a
nozzle 12 with a heat-resistant, sealless ball valve or plug tap for venting overpressure, - a
nozzle 13 for the connection of a vacuum pump for evacuating the retort, - a
nozzle 7 for introducing protective gas, such as argon, from a pipe, - a
nozzle 8 for introducing reactive gases, such as H 2 or N 2 , from a pipe, - a nozzle 9 for receiving a safety valve (p = 0.25 bar),
- a
nozzle 11 for connection to a vacuum and pressure gauge, (of a monometer, 0.1 - 1500 mbar), - a
nozzle 10 for passing one or more thermocouples (Pt / RhPt), - the
water cooling 6 and - optionally a groove for receiving a sealing ring, preferably Viton, if not present on the retort crucible. The
water cooling 6 may be configured, for example, as extending on thelid 5 annular channel. Thecover 5 can preferably be connected via ascrew 19 with theflange 2.
Gemäß der
Der Innentiegel 14 dient gemäß der
Ein besonderes Merkmal besteht in der Ausführung der Kühlung an Deckel 5 und Flansch 2 der Reduktionsretorte. Deckel 5 und Retortentiegel 1 werden durch einen Dichtungsring 4 aus Viton, Perbunan, Teflon oder anderen gebräuchlichen Dichtungswerkstoffen gasdicht und vakuumdicht verbunden. Die Dichtungen 4 können als Flachring oder als O-Ring ausgeführt sein. Die Dichtungen 4 müssen gekühlt werden, da sie bei den hohen Reaktionstemperaturen zersetzt würden. Die Kühlung erfolgt bei dieser Ausführungsvariante mit Wasser. Es wäre katastrophal, wenn Wasser während der Reduktionsreaktion durch Risse oder Korrosionslöcher in den Retortenraum gelangte. Dies würde zu einer heftigen Wasserstoffentwicklung und einer Explosion der Retorte führen. Die Konstruktion der Kühlung ist daher ein ganz wesentliches Merkmal des Reaktionsgefäßes. Die Kühlung 3 am Tiegelflansch ist unten auf den Flansch 2 aufgesetzt und hat nur eine Verbindung zum Flansch selbst, nicht aber zur Retortenwand. So kann aus diesem Bereich niemals Wasser in die Retorte eindringen. Am Deckel 5 ist die Kühlung so ausgeführt, dass sie nur die Fläche des Deckels 5 kühlt, jedoch keine Verbindung zu den Stutzen und Durchführungen hat. Das Kühlwasser müßte durch den massiven Deckel 5 dringen, um in die Retorte zu gelangen, was bei einer Wandstärke von mind. 30 mm hitzefestem Stahl sehr unwahrscheinlich ist. Die Kühlung ist als Wasserkühlung 6 in
Verbunden werden Retortentiegel und Retortendeckel mit einer geeigneten Anzahl von Schrauben und Muttern 19. Die aus dem Retortendeckel 5 und Retortentiegel 1 bestehende Retorte kann nach Entnahme des Innentiegels 14 mit der ausreagierten und phlegmatisierten Masse umgehend wieder zur Aufnahme eines anderen Innentiegels mit einem neuen Ansatz eingesetzt werden. In einem Ofen können somit mehrere Retorten nacheinander zur Reaktion gebracht werden.The retort crucible and retort lid are connected with a suitable number of screws and nuts 19. The
Die in den Abbildungen angegebenen Maße sind geeignet für eine Retorte zur Durchführung der Beispiele, d.h. für die Gewinnung von etwa 25 kg Metallpulver / Ansatz.The dimensions given in the figures are suitable for a retort for carrying out the examples, i. for the recovery of about 25 kg of metal powder / batch.
Ein Beispiel für eine metallothermische Reduktion unter Anwendung der genannten Grundsätze und die vorliegende Erfindung ist die Gewinnung von Zirkonium in Pulverform durch Reduktion von Zirkoniumoxid mit Calcium für Anwendungen in der Gettertechnik (Lampen, Vakuumbauteile) und der militärischen Pyrotechnik, z.B. zur Herstellung von Thermalbatterien.An example of a metallothermal reduction using the above principles and the present invention is the recovery of zirconium in powder form by reduction of zirconium oxide with calcium for use in gettering (lamps, vacuum components) and military pyrotechnics, e.g. for the production of thermal batteries.
Es wird Zirkoniumoxid mit einer mittleren Korngröße von 5 +/- 0,5 Mikrometer, gemessen nach der Blaine Methode oder dem Fisher Sub Sieve Sizer Verfahren, mit Calciumspänen oder Granalien von 0,5 bis 5 mm Größe vermischt. Calciummetall wird in der theoretisch notwendigen stöchiometrischen Menge zugesetzt. Zur Steuerung der Reduktionsreaktion wird zusätzlich eine kleine Menge, z.B. 2 bis 10 Gew.% der theoretisch notwendigen stöchiometrischen Menge an Magnesiumspänen ähnlicher Größe wie des Calciums zugesetzt. Grundsätzlich können weitere Zusätze, etwa Kohlenstoff, Silizium oder Siliziumoxid und andere Stoffe zugefügt werden, um die Eigenschaften des bei der Reduktion entstehenden Zirkoniumpulvers zu beeinflussen. Die Menge der gasförmigen Zusätze bemißt sich so, dass sie sich im später isolierten Zirkoniumpulver im Bereich von 500 bis etwa 5000 ppm, bei Feststoffen von mindestens 2000 bis zu 3 % als "Verunreinigung" wiederfinden. Im vorliegenden Beispiel wird eine kleine Menge Siliziumoxid eingesetzt, die als Si - Verunreinigung im isolierten Zirkoniumpulver wieder auftaucht. Die Mischung der Einsatzstoffe erfolgt unter Argon in einem Rhönradmischer, einem Wendelmischer oder einem anderen vergleichbaren Mischorgan für feste Stoffe. Alle Einsatzstoffe müssen peinlich trocken gehalten werden. Durch die Zugabe einer kleinen Menge des zweiten Reduktionsmetalls (Magnesium) erniedrigt sich die Schwelle der Initialzündung, so dass die Reaktionsmischung leichter zur Zündung gebracht wird als bei Verwendung von Calcium alleine. Da Magnesium früher verdampft als Calcium, wird durch die Verdampfung des Magnesiums Wärme aus der Reaktionsmasse entzogen, so dass die Spitzentemperatur der reagierenden Masse begrenzt wird.Zirconia with a mean grain size of 5 +/- 0.5 micron, measured by the Blaine method or the Fisher Sub Sieve Sizer method, is mixed with calcium chips or granules of 0.5 to 5 mm size. Calcium metal is added in the theoretically necessary stoichiometric amount. To control the reduction reaction, a small amount, for example 2 to 10% by weight, of the theoretically necessary stoichiometric amount of magnesium chips of similar size to calcium is additionally added. In principle, further additives, for example carbon, silicon or silicon oxide and other substances can be added in order to influence the properties of the zirconium powder formed during the reduction. The amount of gaseous additives is measured to be in the range of 500 to about 5000 ppm in the later isolated zirconium powder, and "impurity" for solids of at least 2,000 to 3%. In the present example, a small amount of silicon oxide is used, which reappears as Si contamination in the isolated zirconium powder. The mixture of the starting materials is carried out under argon in a Rhönradmischer, a helical mixer or other comparable mixing device for solids. All feedstocks must be kept scrupulously dry. Lowered by the addition of a small amount of the second reducing metal (magnesium) the threshold of the initial ignition, so that the reaction mixture is easier to ignite than when using calcium alone. Since magnesium vaporizes earlier than calcium, the vaporization of magnesium removes heat from the reaction mass, thereby limiting the peak temperature of the reacting mass.
Durch Zusatz von 3 bis 15 Gew. % Calciumoxid (Branntkalk) oder von nicht gesintertem Magnesiumoxid könnte man auch - alternativ - die Reaktionsmasse verdünnen, die Reaktionsgeschwindigkeit bremsen und die Maximaltemperatur der Reaktion erniedrigen. Diese Verfahrensweise geht aber meistens zu Lasten der Reinheit des zu gewinnenden Zirkoniumpulvers, so dass im vorliegenden Beispiel besser mit Magnesiumzusatz gearbeitet wird.By adding 3 to 15% by weight of calcium oxide (burnt lime) or of non-sintered magnesium oxide, it would also be possible - as an alternative - to dilute the reaction mass, slow down the reaction rate and lower the maximum temperature of the reaction. However, this procedure is usually at the expense of the purity of the zirconium powder to be obtained, so that it is better to use magnesium addition in the present example.
Die Einsatzstoffe werden in einem Fassmischer unter Ar Atmosphäre eingewogen, innig vermischt, in einen Innentiegel umgefüllt und bis zum Einsatz in der erfindungsgemäßen Reduktionsretorte unter Argonatmosphäre trocken gelagert.The starting materials are weighed in a drum mixer under Ar atmosphere, intimately mixed, transferred to an inner crucible and stored dry until used in the reduction of the invention under argon atmosphere.
Zur Durchführung der Reduktionsreaktion wird der Innentiegel mit der Mischung der Einsatzstoffe in den erfindungsgemäßen Retortentiegel eingesetzt, die Retorte durch Aufsetzen des Deckels verschlossen, die gesamte Retorte zweimal auf einen Enddruck von weniger als 1 mbar ausgepumpt zur Entfernung der Luft und etwaiger Feuchtigkeit, und mit Argon geflutet. Über Durchführungen im Deckel wird mindestens ein Thermoelement eingesetzt, um die Temperatur im Reaktionsraum zu messen. Es wird ein Manometer angeschlossen, das sowohl Unterdruck bis 0,1 mbar wie Überdruck bis +1000 mbar anzeigt. Es werden Verbindungen zu Gasdruckflaschen mit Argon, Stickstoff und Wasserstoff hergestellt. Die Gasdruckflaschen sind mit Feindruckminderern ausgestattet, die auf einen max. Druck von 100 mbar eingestellt sind. Die Druckflaschen für Stickstoff und Wasserstoff sind mit abgemessenen Mengen dieser Gase befüllt. Das Schutzgas Argon muss immer in genügender überschüssiger Menge zur Verfügung stehen. Anschließend wird die Reduktion durch Aufheizen der Retorte in einem gasbefeuerten Tiegelofen gestartet. Etwa 45 Minuten später setzt die metallothermische Reduktionsreaktion ein :
ZrO2 + 2 Ca => 2 CaO + Zr
und parallel
ZrO2 + 2 Mg => 2 MgO + Zr
To carry out the reduction reaction, the inner crucible with the mixture of feedstocks in the retort crucible according to the invention is used, the retort closed by placing the lid, the entire retort pumped out twice to a final pressure of less than 1 mbar to remove the air and any moisture, and with argon flooded. Through openings in the lid, at least one thermocouple is used to measure the temperature in the reaction space. It is connected to a pressure gauge, which displays both negative pressure to 0.1 mbar as overpressure to +1000 mbar. Compounds are made to gas pressure bottles with argon, nitrogen and hydrogen. The gas pressure bottles are equipped with fine pressure reducers, which are designed for a max. Print of 100 mbar are set. The pressure cylinders for nitrogen and hydrogen are filled with measured quantities of these gases. The protective gas argon must always be available in sufficient excess quantity. Subsequently, the reduction is started by heating the retort in a gas-fired crucible furnace. About 45 minutes later, the metallothermal reduction reaction starts:
ZrO 2 + 2 Ca => 2 CaO + Zr
and parallel
ZrO 2 + 2 Mg => 2 MgO + Zr
Im vorliegenden Beispiel erfolgt der Reaktionsstart bei einer Temperatur von circa. 100 - 140°C und es werden binnen 2 Minuten 1100°C erreicht. Nach Überschreiten der Spitzentemperatur, erkenntlich am Abfallen der gemessenen Temperatur im Reaktionsraum mittels eines Thermoelements, werden die zur Phlegmatisierung bzw. zur Einstellung der Brenn- und Zündeigenschaften des Zirkoniummetallpulvers notwendigen Gasmengen eingeleitet. Im Beispiel werden 50 Ltr. Stickstoff und 130 Ltr. Wasserstoff aus den angeschlossenen Druckgasflaschen im Lauf der Abkühlphase zugegeben. Dies entspricht einer Menge von 500 ppm Wasserstoff und 2500 ppm Stickstoff im entstandenen Zirkoniummetallpulver. Die Gase werden in der Abkühlphase rasch vom Zirkoniummetall absorbiert. Sind alle Gase zugegeben, erfolgt der weitere erforderliche Druckausgleich während der Abkühlung durch Zugabe von Argon. Nach dem Abkühlen der Retorte auf etwa 600°C im abgeschalteten Ofen wird die Retorte aus dem Reduktionsofen entnommen und in ein Abkühlgestell umgehängt, wo sie über unter weiterer Argonzufuhr auf RT abkühlen kann. Der Reduktionsofen wird frei und kann zum Heizen und Zünden einer weiteren, in der Zwischenzeit vorbereiteten Reduktionsmischung in einer zweiten erfindungsgemäßen Retorte eingesetzt werden.In the present example, the reaction starts at a temperature of about. 100 - 140 ° C and 1100 ° C are reached within 2 minutes. After exceeding the peak temperature, recognizable by the falling of the measured temperature in the reaction space by means of a thermocouple, the necessary for phlegmatization or for adjusting the burning and ignition properties of the zirconium metal powder gas quantities are introduced. In the example, 50 liters of nitrogen and 130 liters of hydrogen from the connected compressed gas cylinders are added in the course of the cooling phase. This corresponds to an amount of 500 ppm of hydrogen and 2500 ppm of nitrogen in the resulting zirconium metal powder. The gases are rapidly absorbed by the zirconium metal during the cooling phase. When all the gases have been added, further pressure equalization takes place during cooling by addition of argon. After cooling the retort to about 600 ° C in the oven switched off the retort is removed from the reduction furnace and transferred to a cooling rack, where it can cool to RT with further argon supply. The reduction furnace is released and can be used for heating and igniting a further, in the meantime prepared reduction mixture in a second retort according to the invention.
Nach vollständiger Abkühlung wird der Innentiegel mit der Reaktionsmasse aus der Retorte entnommen, die Reaktionsmasse herausgebrochen, mit einem Backenbrecher zerkleinert und in Salzsäure gelaugt. Dabei werden Magnesiumoxid und Calciumoxid zu den entsprechenden Chloriden umgesetzt und ausgewaschen. Zurück bleibt ein Metallschlamm aus feinem Zirkoniummetallpulver, dessen Korngröße etwa der des eingesetzten Zirkoniumoxids entspricht, also 5 +/- 1 µm gemessen nach Blaine oder Fisher. Das Metallpulver wird ausgewaschen, nass gesiebt (< 45 µm) und vorsichtig (< 80°C) getrocknet. Aufgrund der zugesetzten Hilfsstoffe (hier SiO2) und der Gase, hier N2 und Wasserstoff, kann das Metallpulver gefahrlos in Wasser und Säure aufbereitet werden, ohne dass eine Reaktion mit Wasser eintritt, und es kann später ohne spontane Selbstentzündung an Luft gehandhabt werden. Die Ausbeute beträgt 25 - 26 kg eines feinen, grauen Zirkoniummetallpulvers.After complete cooling, the inner crucible with the reaction mass is removed from the retort, the reaction mass broken out, crushed with a jaw crusher and leached in hydrochloric acid. In this case, magnesium oxide and calcium oxide are converted to the corresponding chlorides and washed out. What remains is a metal slurry of fine zirconium metal powder, whose Grain size about that of the zirconium oxide used,
Die Brenngeschwindigkeit des so erhaltenen Metallpulvers wird wie folgt gemessen: in einen Stahlblock von 60 cm Länge, 1 cm Höhe und 4 cm Breite wird durchgehend eine rechteckige Rinne eingefräst, die 2 mm tief und 3 mm breit ist. Die Rinne wird mit 15 g des zu prüfenden Metallpulvers gefüllt, die Pulverfüllung wird an einem Ende entzündet und die Zeit gemessen, die die brennende Front benötigt um eine markierte Strecke von 500 mm Distanz zu durchlaufen. Im vorliegenden Fall beträgt die Brennzeit 80 +/- 10 Sekunden / 50 cm. Die Zündtemperatur liegt bei 240 +/- 20 °C. Die elektrische Energie zur Zündung betragt ca. 18 µJ. Im Endprodukt findet man, bedingt durch eine weitere Wasserstoffaufnahme bei der wässrigen Aufarbeitung, insgesamt 2000 ppm Wasserstoff. Auch Verunreinigungen der Reduktionsmetalle finden sich in den Metallpulvern, allerdings sind diese Mengen i.a. gering. Die gefundene Menge von 1800 ppm Silicium, 2500 ppm Stickstoff und 1000 ppm Titan entspricht recht gut der theoretischen Menge.The burning rate of the metal powder thus obtained is measured as follows: into a steel block of 60 cm in length, 1 cm in height and 4 cm in width, a rectangular gutter, which is 2 mm deep and 3 mm wide, is continuously milled. The trough is filled with 15 g of the metal powder to be tested, the powder filling is ignited at one end and the time taken for the burning front to go through a marked distance of 500 mm distance is measured. In the present case, the burning time is 80 +/- 10 seconds / 50 cm. The ignition temperature is 240 +/- 20 ° C. The electrical energy for ignition is about 18 μJ. In the final product can be found due to a further hydrogen uptake in the aqueous workup, a total of 2000 ppm of hydrogen. Also impurities of the reduction metals are found in the metal powders, but these amounts i.a. low. The found amount of 1800 ppm silicon, 2500 ppm nitrogen and 1000 ppm titanium corresponds quite well to the theoretical amount.
Bei einer Abwandlung der Verfahrensweise von Beispiel (1) wird die Retorte nach erfolgter Reduktionsreaktion mit der reagierten Masse im Reduktionsofen belassen. Durch weiteres Heizen von außen wird Einfluss auf die Korngröße des seltenen Metalls bzw. dessen Brenneigenschaften und chemische Eigenschaften genommen. Durch ein mehrstündiges Heizen bei ca. 900°C kann ein Sinterungseffekt erzielt werden, der zu einer Kornvergröberung des gewonnenen Zirkoniummetalls führt. Im vorliegenden Beispiel kann man durch 3 - 4 stündiges Heizen die mittlere Korngröße des Zirkoniummetalls von ca. 5 µm auf 6 - 7 µm erhöhen und die Brenngeschwindigkeit von ca. 75 s / 50 cm auf 100 bis 120 s / 50 cm verlangsamen. Der Zündpunkt des Metalls bleibt bei dieser Verfahrensweise nahezu unverändert und liegt bei 250°C +/- 20°C.In a modification of the procedure of Example (1), the retort is left in the reduction furnace after the reduction reaction with the reacted mass. Further heating from outside influences the grain size of the rare metal or its burning properties and chemical properties. By heating for several hours at about 900 ° C, a sintering effect can be achieved, which leads to a grain coarsening of the zirconium metal obtained. In the present example, by heating for 3-4 hours, the mean grain size of the zirconium metal can be increased from approximately 5 μm to 6 to 7 μm and the burning rate can be slowed from approximately 75 s / 50 cm to 100 to 120 s / 50 cm. The ignition point of the metal remains almost unchanged in this procedure and is at 250 ° C +/- 20 ° C.
Zur Herstellung von Zirkoniummetall, das geeignet ist für die Verwendung in Zündsystemen von Airbag Zündern und militärisch genutzten Zündsätzen wird wie in Beispiel (1) vorgegangen, jedoch werden folgende Einsatzstoffe verwendet:
Die Einsatzstoffe werden wie in Beispiel (1) gemischt, in den Innentiegel gefüllt und in die Retorte eingesetzt. Anders als in Beispiel (1) wird die Retorte zweimal ausgepumpt und danach mit 100 I Wasserstoff, 50 I Stickstoff und Rest Argon aufgefüllt. Nach dem Aufheizen startet die Reduktionsreaktion bei Erreichen einer Temperatur von 150°C +/- 20 °C und erreicht einen Maximalwert von 960 bis 1050°C nach der Gleichung
ZrO2 + 2 Mg => 2 MgO + Zr
The starting materials are mixed as in Example (1), filled in the inner crucible and inserted into the retort. Unlike in Example (1), the retort is pumped out twice and then filled with 100 l of hydrogen, 50 l of nitrogen and the remainder of argon. After heating, the reduction reaction starts when reaching a temperature of 150 ° C +/- 20 ° C and reaches a maximum value of 960 to 1050 ° C according to the equation
In der Abkühlphase werden nochmals 150 I Wasserstoff und 50 I Stickstoff zur Phlegmatisierung des Zirkoniummetallpulvers zugesetzt. Der letzte Druckausgleich beim Abkühlen erfolgt mit Argon. Nach dem Ausbrechen der erkalteten Reaktionsmasse und nach Laugung mit Salzsäure, Waschen, nass sieben unter 45 µm und Trocknen erhält man ein sehr feines, zündwilliges Metallpulver, das an Luft wegen der Phlegmatisierung jedoch nicht selbstentzündlich ist. Beim Waschen wird mehrfach dekantiert, um feinste, in Schwebe befindliche Metallpartikel mit Korngrößen unter 0,2 µm zu entfernen. Die Ausbeute beträgt ca. 25 kg. Das Metallpulver kann vorsichtig bei Temperaturen unter 70°C getrocknet werden.In the cooling phase, another 150 l of hydrogen and 50 l of nitrogen are added to the phlegmatization of the zirconium metal powder. The last pressure equalization on cooling is done with argon. After breaking the cooled reaction mass and after leaching with hydrochloric acid, washing, wet seven below 45 microns and drying to obtain a very fine, ignitable metal powder, which is not selbstentzündlich in air because of phlegmatization. When washing is decanted several times to remove the finest suspended metal particles with particle sizes below 0.2 microns. The yield is about 25 kg. The metal powder can be dried carefully at temperatures below 70 ° C.
Die Brenngeschwindigkeit in einer Rinne (vgl. Beispiel (1) an Luft beträgt 10 +/-3 s/50 cm. Die mittlere Korngröße des Metallpulvers beträgt 1,7 +/- 0,3 µm. Der Zündpunkt liegt bei 180 +/-10 °C. Die elektrische Mindestzündenergie wurde mit ca. 2 µJ gemssen.The burning rate in a gutter (compare Example (1) in air is 10 +/- 3 s / 50 cm.) The mean grain size of the metal powder is 1.7 +/- 0.3 μm Ignition point is 180 +/- 10 ° C. The minimum electrical ignition energy was measured at about 2 μJ.
Der Gehalt an Silizium entspricht etwa dem Einsatz und liegt bei 5900 ppm (theor. 6530 ppm). Der Wasserstoffgehalt liegt im Endprodukt bei 1400 ppm (theor. 900 ppm), bedingt durch eine weitere Wasserstoffaufnahme bei der Säurelaugung. Der Stickstoffgehalt im Endprodukt liegt bei 4000 ppm (theor. 5000 ppm).The content of silicon corresponds approximately to the use and is 5900 ppm (theor. 6530 ppm). The hydrogen content in the final product is 1400 ppm (theor. 900 ppm), due to a further hydrogen uptake in the acid leaching. The nitrogen content in the final product is 4000 ppm (theoretical 5000 ppm).
Die hohe Zündwilligkeit des Metallpulvers resultiert aus der hohen Feinheit und der großen Empfindlichkeit gegen elektrostatische Aufladung. Diese Metallpulver werden im Allgemeinen nicht getrocknet, sondern in Suspension unter mindestens 30 Gew. % Wasser gelagert und gehandelt.The high degree of ignitability of the metal powder results from the high degree of fineness and the high sensitivity to electrostatic charging. These metal powders are generally not dried, but stored and traded in suspension under at least 30% by weight of water.
Es wird wie in Beispiel (1) vorgegangen, jedoch ohne Zusätze von SiO2 und TiO2.
Die Umsetzung erfolgt wie in Beispiel (1), jedoch wird die Retorte nach dem Auspumpen nicht mit Argon, sondern mit 100 I Stickstoff (99,995) befüllt. Durch Aufheizen wird die Umsetzung in Gang gesetzt, sie startet in diesem Fall bereits bei 80 bis 100°C und erreicht einen Spitzenwert von ca. 1050°C.The reaction is carried out as in Example (1), but the retort is filled after pumping not with argon, but with 100 l of nitrogen (99,995). By heating, the reaction is started, it starts in this case already at 80 to 100 ° C and reaches a peak of about 1050 ° C.
Während der Abkühlung werden zur Phlegmatisierung des Zirkoniummetalls weitere 100 Ltr. Stickstoff in die Retorte eingeleitet, der weitere Druckausgleich erfolgt durch Argon.During cooling, a further 100 liters of nitrogen are introduced into the retort for phlegmatization of the zirconium metal, and further pressure is compensated by argon.
Nach dem vollständigen Erkalten wird die Reaktionsmasse ausgebrochen, zerkleinert aber nicht gelaugt, sondern unter Argonatmosphäre und Ausschluss von Feuchtigkeit fein gemahlen auf eine Körnung unter 150 µm. Zu dieser Masse aus Zr-Metall, Calciumoxid und Magnesiumoxid sowie noch überschüssigem Magnesium und Calcium werden 12 kg Nickelpulver (mittlere Korngröße nach Fsss 5 µm) zugefügt (Achtung, Ni-Pulver sind cancerogen) und unter Argonatmosphäre in einem Fassmischer untergemischt. Die Masse wird anschließend in den Innentiegel gefüllt, in die erfindungsgemäße Retorte eingesetzt, evakuiert und unter Argonatmosphäre langsam aufgeheizt, wobei die Ofentemperatur auf 860°C begrenzt wird. Die Ofentemperatur wird nach etwa 1 h erreicht, die Innentemperatur gemessen in der Reaktionsmischung beginnt erst nach ca. 3 bis 5 h zu steigen, sie läuft dann innerhalb von 15 Minuten von ca. 400°C auf 880 -900 °C. Die Heizung wird abgeschaltet, sobald die Umsetzung in Gang kommt. Bei der Reaktion wird das im Nickelpulver stets enthaltene Nickeloxid durch den Reduktionsmittelüberschuss, der in der Zr-Reduktionsmasse noch enthalten ist, zu Ni reduziert und gleichzeitig verbindet sich das Zr-Pulver mit dem Nickel zu einer Zr-Ni-Legierung mit einer Zusammensetzung von 70 Gew. % Zr und 30 Gew. % Nickel. In der Abkühlphase werden 200 I Wasserstoff zugegeben.After complete cooling, the reaction mass is broken, but not crushed leached, but finely ground under Argon atmosphere and exclusion of moisture to a particle size below 150 microns. To this mass out Zr metal, calcium oxide and magnesium oxide as well as excess magnesium and calcium are added to 12 kg nickel powder (mean particle size after
Die Reaktionsmasse läßt man über Nacht in der Retorte in einem Auskühlgestell unter Argonzufuhr erkalten. Nach Öffnen wird die Masse ausgebrochen, zerkleinert und in Säure gelaugt, um Calcium- und Magnesiumoxid auszuwaschen. In diesem Fall muss die Laugung in einer stark acetatgepufferten Salzsäure durchgeführt werden, da die ZrNi-Legierung durch reine Salzsäure angegriffen würde. Die als Suspension zurück bleibende Zr/Ni-Legierung wird nass gesiebt (< 45 µm) und getrocknet.The reaction mass is allowed to cool overnight in the retort in a cooling rack under argon supply. After opening, the mass is broken up, crushed and leached in acid to wash out calcium and magnesium oxide. In this case, the leaching must be carried out in a strongly acetate-buffered hydrochloric acid, since the ZrNi alloy would be attacked by pure hydrochloric acid. The remaining as a suspension Zr / Ni alloy is wet sieved (<45 microns) and dried.
Das erhaltene Zr-Ni-Legierungspulver hat eine Korngröße von 4 - 6 µm gemessen nach Blaine oder Fisher. Die Ausbeute beträgt ca. 36 kg. Die eine Brennzeit liegt bei 200 +/- 30 s / 50 cm gemessen in der in Beispiel (1) beschriebenen Brennrinne. Der Zündpunkt liegt bei 260 - 280°C, der Wasserstoffgehalt bei 0,2 % (2000 ppm) gegenüber 500 ppm theoretisch. Auch hier zeigt sich, dass Wasserstoff bei der chemischen Aufbereitung in Säure gebildet und vom Metall aufgenommen wird. Der Stickstoffgehalt wurde nicht ermittelt, theoretisch liegt er bei 1 %. (10000 ppm). Als elektrische Mindestzündenergie wurde ca. 100 µJ ermittelt.The obtained Zr-Ni alloy powder has a grain size of 4-6 μm measured according to Blaine or Fisher. The yield is about 36 kg. The one burning time is 200 +/- 30 s / 50 cm measured in the hearth described in Example (1). The ignition point is 260-280 ° C, the hydrogen content at 0.2% (2000 ppm) versus 500 ppm theoretically. Here, too, it turns out that hydrogen is formed in acid during chemical treatment and absorbed by the metal. The nitrogen content was not determined, theoretically it is 1%. (10,000 ppm). As electrical minimum ignition energy was determined about 100 μJ.
Das Legierungspulver eignet sich zur Herstellung von Verzögerungszündsätzen nach der US Spezifikation MIL-Z-114108.The alloy powder is suitable for the production of delay igniters according to US specification MIL-Z-114108.
Die in den geschilderten Beispielen hergestellten Zirkoniummetallpulver sind erfindungsgemäß phlegmatisiert und nicht spontan selbstentzündlich, d.h. bei Zutritt von Luft handhabbar. Durch Auswaschen submikroskopisch kleiner Teilchen unter 0,2 µm Korngröße etwa durch Dekantieren während des Laugens und Waschens kann die Zündwilligkeit weiter reduziert werden. Auch die wässrige Aufarbeitung selbst trägt zur Passivierung der Metalloberfläche bei. Letzteres führt aber auch dazu, dass sich Zr-, Ti- und Hf- Metallpulver mit einem dünnen Oxidfilm umgeben und dadurch elektrostatisch aufgeladen werden können. Es kann dann eine spontane Entzündung eintreten, die nicht auf der "klassischen" Selbstentzündlichkeit beruht sondern auf eine elektrostatische Entladung zurückzuführen ist. Zr-, Ti- und Hafnium - Metallpulver müssen daher immer in geerdeten, möglichst metallischen Gefäßen gehandhabt werden und soweit als möglich unter Argon verarbeitet werden. Bei der Nacharbeit der in der Erfindung angegeben Beispiele sind entsprechende Sicherheitsmaßnahmen zu treffen und es sollte professionelle Beratung durch ausgebildete Sicherheitsfachkräfte eingeholt werden.The zirconium metal powder produced in the examples described are phlegmatized according to the invention and are not spontaneously self-ignitable, ie manageable upon access of air. By washing out submicroscopic particles smaller than 0.2 microns grain size, for example by decantation during leaching and washing, the ignitability can be further reduced. The aqueous workup itself also contributes to the passivation of the metal surface. However, the latter also leads to the fact that Zr, Ti and Hf metal powders are surrounded by a thin oxide film and can thus be charged electrostatically. It can then enter a spontaneous inflammation, which is not based on the "classic" Selbstentzündlichkeit but is due to an electrostatic discharge. Zr, Ti and hafnium - metal powders must therefore always be handled in grounded, preferably metallic vessels and processed as far as possible under argon. When reworking the examples given in the invention, appropriate safety measures must be taken and professional advice should be obtained from trained safety experts.
- 11
- Retortentiegelretort crucible
- 22
- Flanschflange
- 33
- Kühlung am TiegelflanschCooling at the crucible flange
- 44
- Dichtung (O - Ring oder Flachband)Seal (O - ring or flat band)
- 55
- Deckelcover
- 66
- Wasserkühlungwater cooling
- 77
- Stutzen zum Einleiten von Schutzgas (Argonanschluß)Nozzle for introducing protective gas (argon connection)
- 88th
- Stutzen zum Einleiten von H2, N2 und anderer reaktiver GaseNozzle for introducing H 2 , N 2 and other reactive gases
- 99
- Stutzen zur Aufnahme eines SicherheitsventilsNozzle for receiving a safety valve
- 1010
- Stutzen zum Durchführen eines oder mehrerer Thermoelemente ThermoelementNozzle for passing one or more thermocouples Thermocouple
- 1111
- Stutzen zum Anschluss eines Vakuum- und Druckmessgeräts (Manometer)Connecting piece for connecting a vacuum and pressure gauge (manometer)
- 1212
- Stutzen für Druckablassventil (Kugelhahn o. Kükenhahn, dichtungslos)Nozzle for pressure relief valve (ball valve or plug, sealless)
- 1313
- Stutzen für Anschluss einer VakuumpumpeNozzle for connection of a vacuum pump
- 1414
- Innentiegelinner pot
- 1515
- Ansatzmischungbatch mixture
- 16.116.1
- Heizung (Elektrizität)Heating (electricity)
- 16.216.2
- Heizung (Gas)Heating (gas)
- 1717
- beheizbarer Reduktionsofenheatable reduction furnace
- 1818
- Ofenraum / BrennkammerOven space / combustion chamber
- 1919
- Verschraubungscrew
- 2020
- Distanzhalter mit StützringSpacer with support ring
- 2121
- Schutzrohr für ThermoelementProtective tube for thermocouple
Claims (17)
- Method for manufacturing desensitised metal powder or alloy powder with an average grain size smaller than 10 µm, consisting of or containing at least one of the readily reactive metals zirconium, titanium or hafnium, by metallothermic reduction of oxides or halides of said readily reactive metals with the aid of a reduction metal, characterised in that the metal powder or alloy powder- is desensitised by the addition of a passivating gas or gas mixture during and/or after the oxides or halides are reduced, wherein nitrogen in a quantity of at least 1000 ppm and/or hydrogen in a minimum quantity of 500 ppm are introduced into the metal powder or alloy powder as the passivating gas and/or- is desensitised before the oxides or halides are reduced by the further addition of at least 2000 ppm (0.2% by weight) and not more than 30000 ppm (3% by weight) of a passivating solid,wherein both the reduction and the desensitisation are conducted in a gas-tight reaction vessel in which a vacuum can be established.
- Method according to claim 1, characterised in that nitrogen is introduced into the metal powder or alloy powder in a quantity of 2000 - 3000 ppm as the passivating gas.
- Method according to either of claims 1 or 2, characterised in that nitrogen and hydrogen are introduced in the form of ammonia.
- Method according to claim 1, characterised in that carbon is introduced via the gas phase in the form of methane, carbon dioxide or carbon monoxide.
- Method according to any one of claims 1 to 4, characterised in that the passivating gases are fed into the reaction vessel while the fully reacted mass is cooling after reaching the peak temperature.
- Method according to claim 1, characterised in that carbon, silicon, boron, nickel, chromium and/or aluminium is/are introduced as the passivating solid; and/or the passivating solid is introduced in the form of a fine powder of the elements Ni, Cr, Al, Si, B or C having an average grain size smaller than 20 µm.
- Method according to claim 6, characterised in that the passivating solid is introduced in the form of a fine oxide of the elements Ni, Cr, Al, Si and B having an average grain size smaller than 20 µm and is reduced together with the metal oxide.
- Method according to any one of claims 1 to 7, characterised in that the combustibility of the desensitised metal powders or alloy powders is reduced further by washing out submicroscopically small particles having a grain size smaller than 0.2 µm during leaching and/or washing.
- Desensitised metal powder or alloy powder having an average grain size smaller than 10 µm, measured according to permeability methods such as the Blaine or Fisher method, consisting of or containing the readily reactive metals zirconium, titanium or hafnium, produced by metallothermic reduction of oxides or halides of said metals with the aid of calcium or magnesium as the reduction metal and with the addition of passivating gases such as nitrogen and/or hydrogen and/or of a passivating solid, prepared and isolated by leaching in aqueous acids, wherein the metal powder or alloy powder contains nitrogen in a quantity of at least 1000 ppm and/or hydrogen in a minimum quantity of 500 ppm as the passivating gas, and/or the additionally introduced passivating solid in a proportion of at least 2000 ppm (0.2% by weight) and not more than 30000 ppm (3% by weight).
- Metal powder or alloy powder according to claim 9, characterised in that the metal powder or alloy powder contains nitrogen in a quantity from 2000 to 3000 ppm and/or hydrogen in a quantity from 1000 to 2000 ppm as the passivating gas.
- Metal powder or alloy powder according to either of claims 9 or 10, characterised in that nitrogen or hydrogen were introduced into the metal powder or alloy powder via the gas phase in the form of ammonia.
- Metal powder or alloy powder according to either of claims 9 or 10, characterised in that carbon was introduced into the metal powder or alloy powder via the gas phase in the form of methane, carbon dioxide or carbon monoxide, or that the metal powder or alloy powder contains carbon, silicon, boron, nickel, chromium and/or aluminium as a passivating solid.
- Metal powder or alloy powder according to claim 12, characterised in that the passivating solid was introduced in the form of a fine oxide of the elements Ni, Cr, Al, Si and B having an average grain size smaller than 20 µm, and reduced together with the metal oxide; or the passivating was introduced in the form of a fine powder of the elements Ni, Cr, Al, Si, B or C having an average grain size smaller than 20 µm.
- Metal powder or alloy powder according to any one of claims 9 to 13, characterised in that the passivating gases and solids were introduced together.
- Metal powder or alloy powder with an average grain size smaller than 10 µm, consisting of or containing at least one of the readily reactive metals zirconium, titanium or hafnium, wherein the metal powder or alloy powder was prepared by metallothermic reduction of oxides or halides of said readily reactive metals with the aid of calcium or magnesium as the reduction metal in a method according to any one of claims 1 to 8.
- Use of a metal powder or alloy powder with an average grain size smaller than 10 µm, consisting of or containing at least one of the readily reactive zirconium, titanium or hafnium and prepared by metallothermic reduction of oxides or halides of said readily reactive metals with the aid of a reduction metal in a method according to any one of claims 1 to 8 in powder metallurgy, pyrotechnics or as a getter substance in vacuum technology.
- Use of a metal powder or alloy powder according to claim 16 in the production of time-delayed priming charges.
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EP11180240.1A EP2394762B1 (en) | 2008-01-23 | 2009-01-08 | Reaction vessel for the production of phlegmatized metal powder or alloy powder |
PL11180240T PL2394762T3 (en) | 2008-01-23 | 2009-01-08 | Reaction vessel for the production of phlegmatized metal powder or alloy powder |
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DE102008005781A DE102008005781A1 (en) | 2008-01-23 | 2008-01-23 | Phlegmatized metal powder or alloy powder and method or reaction vessel for the production thereof |
PCT/EP2009/050163 WO2009092631A1 (en) | 2008-01-23 | 2009-01-08 | Phlegmatized metal powder or alloy powder and method and reaction vessel for the production thereof |
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EP (2) | EP2394762B1 (en) |
JP (2) | JP5876651B2 (en) |
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CN (1) | CN101925427B (en) |
AU (1) | AU2009207739B2 (en) |
BR (1) | BRPI0907383A2 (en) |
CA (1) | CA2712929C (en) |
DE (2) | DE102008005781A1 (en) |
IL (2) | IL206966A (en) |
MX (1) | MX2010007826A (en) |
MY (1) | MY152942A (en) |
PL (1) | PL2394762T3 (en) |
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008005781A1 (en) * | 2008-01-23 | 2009-07-30 | Tradium Gmbh | Phlegmatized metal powder or alloy powder and method or reaction vessel for the production thereof |
DE102008000433A1 (en) * | 2008-02-28 | 2009-09-03 | Chemetall Gmbh | Process for the production of alloy powders based on titanium, zirconium and hafnium alloyed with the elements Ni, Cu, Ta, W, Re, Os and Ir |
JP2014518334A (en) * | 2011-07-01 | 2014-07-28 | ゼネラル・エレクトリック・カンパニイ | Continuous production method of titanium alloy powder |
GB201218675D0 (en) | 2012-10-17 | 2012-11-28 | Univ Bradford | Improved method for metal production |
KR101494340B1 (en) * | 2013-08-27 | 2015-03-04 | 주식회사 나노테크 | method of preparing titanium carbide powder |
AT13691U1 (en) * | 2013-09-02 | 2014-06-15 | Plansee Se | Chromium metal powder |
KR101691410B1 (en) | 2014-08-13 | 2017-01-02 | 주식회사 나노테크 | Method for Preparing Titanium Carbonitride Powder |
AP2017009844A0 (en) * | 2014-09-09 | 2017-03-31 | Univ Arizona | A system, apparatus, and process for leaching metal and storing thermal energy during metal extraction |
WO2016041063A1 (en) * | 2014-09-15 | 2016-03-24 | Materiaux Nieka Inc. | Method and apparatus for preparing an analytical sample by fusion |
US10455680B2 (en) | 2016-02-29 | 2019-10-22 | Asml Netherlands B.V. | Method and apparatus for purifying target material for EUV light source |
KR102475050B1 (en) | 2016-04-11 | 2022-12-06 | 에이피앤드씨 어드밴스드 파우더스 앤드 코팅스 인크. | Reactive Metal Powder Air Thermal Treatment Processes |
RU2638869C1 (en) * | 2016-10-11 | 2017-12-18 | федеральное государственное бюджетное образовательное учреждение высшего образования "Ульяновский государственный технический университет" | Method of producing protective oxide film on metallic surface |
RU2634111C1 (en) * | 2016-10-17 | 2017-10-23 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method for disaggregating of naturiethermal zirconium powder |
CN107971500B (en) * | 2017-12-01 | 2020-09-25 | 北京汽车集团越野车有限公司 | Manufacturing method of magnesium alloy part and magnesium alloy part |
CN110319690A (en) * | 2019-07-03 | 2019-10-11 | 宁夏秦氏新材料有限公司 | Gas heating metal nitride synthesis device |
CN110255510A (en) * | 2019-07-03 | 2019-09-20 | 宁夏秦氏新材料有限公司 | The method of gas heating synthesis manganese systems nitride |
CN110319691A (en) * | 2019-07-03 | 2019-10-11 | 宁夏秦氏新材料有限公司 | A kind of gas heating metal nitride synthesis device |
CN110319689A (en) * | 2019-07-03 | 2019-10-11 | 宁夏秦氏新材料有限公司 | A kind of gas heating metal nitride synthesis device |
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CN112458316A (en) * | 2020-11-13 | 2021-03-09 | 云南国钛金属股份有限公司 | Device and method for preventing gas channel of reactor cover from being blocked |
CN113149797A (en) * | 2021-04-29 | 2021-07-23 | 江苏长积材料科技有限公司 | Intrinsic safety type carbon dioxide gasifying agent and preparation method thereof |
CN113996401B (en) * | 2021-11-16 | 2022-09-23 | 湖南先导电子陶瓷科技产业园发展有限公司 | Titanate ceramic powder high temperature rapid synthesis equipment |
CN117419566B (en) * | 2023-12-18 | 2024-03-15 | 河北睿阳稀有金属制品有限公司 | Reduction device for hafnium sponge production |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1526443A (en) * | 1975-02-03 | 1978-09-27 | Ppg Industries Inc | Titanium zirconium or hafnium boride powder and method for preparing same |
Family Cites Families (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE96317C (en) | ||||
US1602542A (en) * | 1921-01-06 | 1926-10-12 | Westinghouse Lamp Co | Reduction of rare-metal oxides |
GB771351A (en) * | 1954-01-19 | 1957-04-03 | Gen Electric Co Ltd | Improvements in or relating to the bright annealing of brass |
US4062679A (en) * | 1973-03-29 | 1977-12-13 | Fansteel Inc. | Embrittlement-resistant tantalum wire |
US3992192A (en) * | 1974-07-01 | 1976-11-16 | Haig Vartanian | Metal powder production |
JPS5452608A (en) | 1977-10-04 | 1979-04-25 | Nippon Mining Co Ltd | Manufacture of zirconium |
US4149876A (en) * | 1978-06-06 | 1979-04-17 | Fansteel Inc. | Process for producing tantalum and columbium powder |
CA1202183A (en) * | 1982-05-31 | 1986-03-25 | Hiroshi Ishizuka | Apparatus and method for producing purified refractory metal from a chloride thereof |
US4470847A (en) * | 1982-11-08 | 1984-09-11 | Occidental Research Corporation | Process for making titanium, zirconium and hafnium-based metal particles for powder metallurgy |
JPH0317197Y2 (en) | 1985-07-17 | 1991-04-11 | ||
CN1015640B (en) * | 1988-05-28 | 1992-02-26 | 中国石油化工总公司石油化工科学研究院 | Supported non-noble metal hydrocracking catalyst |
CN1022579C (en) * | 1988-06-24 | 1993-10-27 | 冶金工业部攀枝花钢铁公司钢铁研究院 | Process for preparing reduced titanite ore powder |
JPH02129314A (en) * | 1988-11-08 | 1990-05-17 | Sumitomo Metal Ind Ltd | Method for cooling connecting part in vacuum refining vessel |
JPH0623556Y2 (en) * | 1989-02-17 | 1994-06-22 | 株式会社神戸製鋼所 | Electroslag remelting furnace |
US5073409A (en) * | 1990-06-28 | 1991-12-17 | The United States Of America As Represented By The Secretary Of The Navy | Environmentally stable metal powders |
JPH05163511A (en) | 1991-12-10 | 1993-06-29 | Mitsui Mining & Smelting Co Ltd | Production of alloy powder |
JPH0688104A (en) | 1992-07-21 | 1994-03-29 | Nippon Steel Corp | Production of titanium powder |
DE4226982C1 (en) | 1992-08-14 | 1993-12-09 | Elektro Thermit Gmbh | Metallothermal reaction mixture |
US5442978A (en) * | 1994-05-19 | 1995-08-22 | H. C. Starck, Inc. | Tantalum production via a reduction of K2TAF7, with diluent salt, with reducing agent provided in a fast series of slug additions |
AU686444B2 (en) * | 1994-08-01 | 1998-02-05 | Kroftt-Brakston International, Inc. | Method of making metals and other elements |
JPH08269502A (en) | 1995-03-28 | 1996-10-15 | Mitsubishi Heavy Ind Ltd | Method for suppressing activity of active metal |
RU2185262C2 (en) * | 1999-08-27 | 2002-07-20 | Российский Федеральный Ядерный Центр - Всероссийский Научно-Исследовательский Институт Экспериментальной Физики | Method for passivation of pyrophoric metallic powders |
CN2515206Y (en) * | 2001-12-15 | 2002-10-09 | 王艳 | Double-pot type metal zirconium reduction device |
JP2004052003A (en) * | 2002-07-16 | 2004-02-19 | Cabot Supermetal Kk | Method and apparatus for producing niobium powder or tantalum powder |
JP2004052033A (en) | 2002-07-18 | 2004-02-19 | Nippon Steel Corp | Button headed high-strength rolled prestressed concrete steel bar and method for manufacturing the same |
US6902601B2 (en) | 2002-09-12 | 2005-06-07 | Millennium Inorganic Chemicals, Inc. | Method of making elemental materials and alloys |
TWI341337B (en) * | 2003-01-07 | 2011-05-01 | Cabot Corp | Powder metallurgy sputtering targets and methods of producing same |
JP2004247177A (en) | 2003-02-13 | 2004-09-02 | Jeol Ltd | Composite plasma generating device |
KR20040074828A (en) * | 2003-02-19 | 2004-08-26 | 한국기계연구원 | Method for manufacturing nanophase tic composite powders by metallothermic reduction |
DE10332033A1 (en) * | 2003-07-15 | 2005-02-03 | Chemetall Gmbh | Process for the preparation of metal powders or of metal hydride powders of the elements Ti, Zr, Hf, V, Nb, Ta and Cr |
US6939389B2 (en) * | 2003-08-08 | 2005-09-06 | Frank Mooney | Method and apparatus for manufacturing fine powders |
BRPI0622420B8 (en) * | 2005-09-16 | 2022-07-12 | Starck H C Gmbh | VALVE METAL POWDER AND USE OF A VALVE METAL POWDER |
JP2007084847A (en) * | 2005-09-20 | 2007-04-05 | Sumitomo Titanium Corp | METHOD AND DEVICE FOR PRODUCING Ti |
CN2934267Y (en) * | 2006-08-07 | 2007-08-15 | 贵阳铝镁设计研究院 | Reactor roof board |
US7753989B2 (en) * | 2006-12-22 | 2010-07-13 | Cristal Us, Inc. | Direct passivation of metal powder |
DE102008005781A1 (en) * | 2008-01-23 | 2009-07-30 | Tradium Gmbh | Phlegmatized metal powder or alloy powder and method or reaction vessel for the production thereof |
-
2008
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1526443A (en) * | 1975-02-03 | 1978-09-27 | Ppg Industries Inc | Titanium zirconium or hafnium boride powder and method for preparing same |
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US20100272999A1 (en) | 2010-10-28 |
PL2394762T3 (en) | 2014-05-30 |
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AU2009207739A1 (en) | 2009-07-30 |
EP2247398A1 (en) | 2010-11-10 |
WO2009092631A1 (en) | 2009-07-30 |
DE102008064648A1 (en) | 2010-05-20 |
EP2394762A1 (en) | 2011-12-14 |
MY152942A (en) | 2014-12-15 |
US8821610B2 (en) | 2014-09-02 |
IL206966A (en) | 2015-06-30 |
UA102086C2 (en) | 2013-06-10 |
US9279617B2 (en) | 2016-03-08 |
JP2014129605A (en) | 2014-07-10 |
IL237346A0 (en) | 2015-04-30 |
CN101925427B (en) | 2014-06-18 |
JP5876651B2 (en) | 2016-03-02 |
IL206966A0 (en) | 2010-12-30 |
BRPI0907383A2 (en) | 2015-07-21 |
JP2011514435A (en) | 2011-05-06 |
AU2009207739B2 (en) | 2013-03-07 |
US20150130121A1 (en) | 2015-05-14 |
KR20100113092A (en) | 2010-10-20 |
RU2492966C2 (en) | 2013-09-20 |
KR101557174B1 (en) | 2015-10-02 |
DE102008005781A1 (en) | 2009-07-30 |
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