EP0861699B1 - Fine iron powder containing phosphorus - Google Patents

Fine iron powder containing phosphorus Download PDF

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Publication number
EP0861699B1
EP0861699B1 EP98102811A EP98102811A EP0861699B1 EP 0861699 B1 EP0861699 B1 EP 0861699B1 EP 98102811 A EP98102811 A EP 98102811A EP 98102811 A EP98102811 A EP 98102811A EP 0861699 B1 EP0861699 B1 EP 0861699B1
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Prior art keywords
iron
phosphorus
finely divided
less
containing iron
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German (de)
French (fr)
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EP0861699A1 (en
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Bernd Leutner
Gabriele Friedrich
Reinhold Schlegel
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BASF SE
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BASF SE
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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
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B22F9/305—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis of metal carbonyls
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0214—Using a mixture of prealloyed powders or a master alloy comprising P or a phosphorus compound

Definitions

  • the invention relates to fine-particle phosphorus-containing iron and a process its manufacture.
  • Iron-phosphorus alloys are formed when metallic iron is heated with elemental phosphorus, in the reduction of compounds of phosphorus in the presence of iron and with the simultaneous reduction of Compounds of iron and phosphorus.
  • the product is obtained as an amorphous, slag-like mass and can contain a high proportion of minor components.
  • An alloy of iron and phosphorus, ferrophosphorus is a by-product in the manufacture of phosphorus in an electric furnace. That in the raw materials The iron oxide contained in the phosphorus extraction is reduced to iron and absorbs phosphorus. Ferrophosphorus, with 20-27% by weight phosphorus, contains 1 to 9% by weight of silicon as a minor component and others Metals like titanium, vanadium, chrome and manganese.
  • GB-A-824 147 discloses a method of manufacture of phosphorus-containing iron, in which phosphorus trichloriol as a phosphorus-containing component with iron pentacarbonyl is implemented.
  • the invention has for its object a method for manufacturing of fine-particle phosphorus-containing iron with a wide range variable phosphorus content and a small proportion of secondary components provide.
  • the invention was based on the object Process for the production of finely divided iron containing phosphorus on the To provide the basis of the process for the production of carbonyl iron powder.
  • the invention is based on known processes for producing phosphorus-containing Iron from a phosphorus and an iron component.
  • the method according to the invention is given in claim 1.
  • Suitable phosphorus compounds are phosphines or alkylphosphines. Examples are phosphine (PH 3 ), diphosphine (P 2 H 4 ), methylphosphine, dimethylphosphine and trimethylphosphine. PH 3 is preferably used.
  • An advantage of the method according to the invention is that Choice of gas composition, the phosphorus content of the finely divided phosphorus-containing Iron powder can vary within wide limits. Basically it is Ratio of iron pentacarbonyl to the phosphorus compound in the gas mixture freely selectable, usually - based on the weight - Iron pentacarbonyl is used in excess. Preferably with an excess of iron pentacarbonyl of at least 10: 1, especially preferably 15: 1, in particular with an excess between 15: 1 and 300: 1 worked.
  • the resulting finely divided iron containing phosphorus can have a phosphorus content have up to 50 wt .-%.
  • the phosphorus content is preferably between 0.1 and 20% by weight.
  • the phosphorus content can be determined by known methods elemental analysis, for example wet chemical, by atomic emission spectroscopy or by X-ray micro-area analysis from SEM images be determined.
  • the reaction can be carried out in a heatable decomposer, for example for the production of carbonyl iron powder by thermal decomposition of iron pentacarbonyl is used and in in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 14, page 599 or in DE 3 428 121 or DE 3 940 347 is carried out.
  • a decomposer comprises a preferably vertically arranged tube a heat-resistant material such as quartz glass or V2A steel, made by a heating device, for example consisting of heating tapes, heating wires or a heating jacket through which a heating medium flows.
  • the heating device for setting a zone is preferably lower Temperature and a zone of higher temperature in at least 2 segments divided.
  • the gases are premixed and preferably from above into the Decomposition pipe initiated, the gas mixture entering the zone of low temperature happened first.
  • the temperature of the hotter (lower) is preferably Pipe section at least 20 ° C above the temperature of the cooler pipe section.
  • the temperature profile set in this way presumably favors the Formation of the finely divided phosphorus-containing iron due to the in the area convective gas flow forming the temperature gradient.
  • the resulting finely divided phosphorus-containing iron can in a separator according to known Method using gravity or centrifugal force and / or be separated using filter devices.
  • the mass of the particles formed is so high that it can easily re-adjust trickle out of the decomposer at the bottom and collected in a receptacle can be.
  • For finer particles that are entrained by the gas flow would be a separation by single or multiple redirection the gas flow in the separator and / or use of suitable filters can be achieved.
  • the reaction is carried out at temperatures above room temperature.
  • the temperature is above 200 ° C, especially preferably between 250 ° C and 375 ° C.
  • the reaction is in the presence of ammonia, which is believed to be the decomposition of iron pentacarbonyl in Accelerated iron and carbon monoxide, performed.
  • ammonia is believed to be the decomposition of iron pentacarbonyl in Accelerated iron and carbon monoxide, performed.
  • the Amount of ammonia in the gas mixture between 0.1 and 10 vol%.
  • the reaction is preferably carried out in the absence of atmospheric Oxygen carried out, working in the presence of additional carrier gases can be.
  • Carbon monoxide is preferred as an additional Carrier gas used.
  • the CO content of the gas mixture is preferably in this case between 10 and 90%.
  • the total pressure during implementation is preferably between 1 and 5 bar, particularly preferred is the reaction carried out at atmospheric pressure.
  • the high advantage of the process according to the invention is particularly advantageous Purity of the finely divided phosphorus-containing iron obtained on the Attributed to the use of particularly pure, gaseous starting materials is.
  • the carbon content is below 1% by weight, the nitrogen content below 1% by weight and the hydrogen content below 0.5 Wt .-%.
  • the phosphorus-containing iron powders obtained according to the invention preferably have the following levels of foreign elements: nickel ⁇ 100 ppm, chromium ⁇ 150 ppm, molybdenum ⁇ 20 ppm, arsenic ⁇ 2 ppm, lead ⁇ 10 ppm, Cadmium ⁇ 1 ppm, copper ⁇ 5 ppm, manganese ⁇ 10 ppm, mercury ⁇ 1 ppm, sulfur ⁇ 10 ppm, silicon ⁇ 10 ppm, zinc ⁇ 10 ppm.
  • the foreign element content can be determined by means of atomic absorption spectral analysis become.
  • the low foreign element content, which is usually below the Detection limit of the atomic absorption spectral analysis is different phosphorus-containing iron produced by the process according to the invention clearly of phosphorus-containing iron produced by known processes.
  • the phosphorus-containing iron in the invention Process in finely divided form and thus a mechanical Aftertreatment, for example by grinding, can be omitted.
  • the fine-particle phosphorus-containing iron either falls as powder consisting essentially of spherical particles or as fine, polycrystalline threads, so-called whiskers.
  • the iron powders containing phosphorus according to the invention essentially consist from spherical particles with an average particle diameter between 0.3 and 20 ⁇ m, preferably between 1 and 10 ⁇ m. Average particle diameter can be photographically or with known methods Scattered light methods, for example with a laser scattered light photometer, be determined.
  • the iron whiskers containing phosphorus according to the invention essentially exist from filiform aggregates of spheres with a diameter of Balls between 1 and 3 ⁇ m.
  • Another advantage of the method according to the invention is that by choice the reaction parameters such as pressure, temperature and flow rate either powder or whiskers can be obtained, furthermore the average particle diameter of the powder by choosing these parameters can be varied.
  • the mechanical properties of phosphorus-iron alloys are determined in particular by their phosphorus content.
  • the invention phosphorus-containing iron powders are therefore particularly advantageous for applications where it depends on the setting of certain mechanical properties how hardness or brittleness is used.
  • Powder metallurgy is a special field of material production and processing, in which Powdery materials on a metallic basis by pressing and / or sintering be connected to form bodies.
  • Preferred applications are, for example compression molding and powder injection molding ("metal injection molding").
  • the fine-particle phosphorus-containing iron according to the invention can by itself or mixed with other metal powders - e.g. made of nickel, cobalt, bronze - be used to manufacture iron alloys.
  • the fine particle according to the invention phosphorus-containing iron, for example, for embedding industrial diamonds in cutting and grinding tools and for the production of metal ceramics, so-called cermets can be used.
  • the apparatus for the thermal decomposition of iron pentacarbonyl [Fe (CO) 5 ] and phosphine (PH 3 ) consists of a decomposition tube of 1 m length and 20 cm inside diameter made of V2A steel.
  • the decomposing tube is heated with heating tapes, a T 2 being set in the bottom third of the tube, which is at least 20 ° C. higher than the temperature T 1 in the upper part of the tube.
  • the liquid Fe (CO) 5 is evaporated in an electrically heated storage vessel and the steam together with PH 3 and CO (approx. 15 l / h) and NH 3 (approx. 1 l / h) are introduced into the decomposition tube from above.
  • the formation of the phosphorus-containing iron powder takes place in the decomposition tube with the release of CO and H 2 .
  • the resulting phosphorus-containing iron powder trickles down out of the decomposer and is collected in a glass flask.
  • the exhaust gas is passed through mercury (II) chloride solution and the precipitate formed is analyzed for phosphorus. Only traces of phosphorus were detected, from which a complete conversion of the PH 3 used can be concluded.
  • the element composition is determined from SEM images using X-ray micro-area analysis. Average particle diameters are determined using a laser scattered light photometer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Disintegrating Or Milling (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Catalysts (AREA)
  • Powder Metallurgy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Luminescent Compositions (AREA)
  • Compounds Of Iron (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

A process for producing finely divided phosphorus-containing iron involves gaseous phase reaction of iron pentacarbonyl with a phosphorus compound, preferably phosphine. Preferably, the reaction is carried out in the presence of ammonia at above 200 degrees C. Also claimed is a finely divided phosphorus-containing iron which consists of spherical particles with 1-10 mu mean particle diameter or of filament aggregates of spheres with 0.2-3 mu diameter. Preferably, the iron contains 0.1-50 wt.% P, less than 1 wt.% C, less than 1 wt.% N, less than 0.5 wt.% H and less than 0.1 wt.% total of other impurity elements and is produced by the above process. Further claimed is apparatus for carrying out the above process, including a heated decomposition tube, devices for producing two different temperature zones, for evaporating liquid iron pentacarbonyl and for gas dosing and mixing, and a separator for finely divided phosphorus-containing iron.

Description

Die Erfindung betrifft feinteiliges phosphorhaltiges Eisen und ein Verfahren zu seiner Herstellung.The invention relates to fine-particle phosphorus-containing iron and a process its manufacture.

Für bestimmte Anwendungen, beispielsweise in der Pulvermetallurgie, werden feine Metallpulver mit definierten mechanischen Eigenschaften benötigt. Für solche Anwendungen besonders geeignet ist sogenanntes Carbonyleisenpulver, das nach einem klassischen Verfahren durch thermische Zersetzung von Eisenpentacarbonyl in der Gasphase hergestellt wird. Die besonders günstigen Eigenschaften, wie die gute Sinterfähigkeit des Pulvers, beruhen auf seiner Reinheit, seiner niedrigen Entstehungstemperatur sowie der geringen Größe, der großen spezifischen Oberfläche und der Kugelform der Pulverteilchen. Durch Verwendung von Fremdelementen als Legierungsbestandteile können, bei möglichst niedrigem Gehalt an weiteren Nebenbestandteilen, die mechanischen Eigenschaften des Pulvers gezielt beeinflußt werden. In Frage kommt hier insbesondere die Verwendung von Phosphor zur Herstellung von Pulvern aus Phosphor-Eisen-Legierung mit definiertem, die Härte oder Sprödigkeit der Pulver und der daraus gefertigten Teile bestimmenden Phosphorgehalt.For certain applications, for example in powder metallurgy fine metal powder with defined mechanical properties is required. For such applications are particularly suitable for so-called carbonyl iron powder, using a classic method by thermal decomposition of iron pentacarbonyl is produced in the gas phase. The most affordable Properties such as the good sinterability of the powder are based on it Purity, its low temperature as well as its small size, the large specific surface area and the spherical shape of the powder particles. By using foreign elements as alloy components, with the lowest possible content of other secondary components, the mechanical Properties of the powder can be influenced in a targeted manner. It is a possibility here in particular the use of phosphorus for the production of powders Made of phosphor iron alloy with defined, the hardness or brittleness the powder and the phosphorus content determining the parts made from it.

In Gmelins Handbuch der Anorganischen Chemie, Band "Eisen", Teil A, Abt. II, 8. Auflage 1934/1939, Seite 1784-85 sind verschiedene klassische Verfahren zur Darstellung von Eisen-Phosphor-Legierungen beschrieben. Eisen-Phosphor-Legierungen entstehen beim Erhitzen von metallischem Eisen mit elementarem Phosphor, bei der Reduktion von Verbindungen des Phosphors in Gegenwart von Eisen sowie bei der gleichzeitigen Reduktion von Verbindungen des Eisens und des Phosphors.In Gmelin's Handbook of Inorganic Chemistry, Volume "Iron", Part A, Dept. II, 8th edition 1934/1939, pages 1784-85 are different classic Methods for the preparation of iron-phosphorus alloys described. Iron-phosphorus alloys are formed when metallic iron is heated with elemental phosphorus, in the reduction of compounds of phosphorus in the presence of iron and with the simultaneous reduction of Compounds of iron and phosphorus.

Bei den dort aufgeführten Verfahren sind zum Teil hohe Reaktionstemperaturen erforderlich. Das Produkt fällt als amorphe, schlackeartige Masse an und kann einen hohen Anteil an Nebenbestandteilen enthalten.Some of the processes listed there involve high reaction temperatures required. The product is obtained as an amorphous, slag-like mass and can contain a high proportion of minor components.

Eine Legierung aus Eisen und Phosphor, Ferrophosphor, entsteht als Nebenprodukt bei der Herstellung von Phosphor im Elektroofen. Das in den Rohmaterialien der Phosphor-Gewinnung enthaltene Eisenoxid wird zu Eisen reduziert und nimmt Phosphor auf. Ferrophosphor, mit 20 - 27 Gew.-% Phosphor, enthält als Nebenbestandteile 1 bis 9 Gew.-% Silizium sowie weitere Metalle wie Titan, Vanadium, Chrom und Mangan.An alloy of iron and phosphorus, ferrophosphorus, is a by-product in the manufacture of phosphorus in an electric furnace. That in the raw materials The iron oxide contained in the phosphorus extraction is reduced to iron and absorbs phosphorus. Ferrophosphorus, with 20-27% by weight phosphorus, contains 1 to 9% by weight of silicon as a minor component and others Metals like titanium, vanadium, chrome and manganese.

Für Anwendungen, bei denen hochreines Eisenpulver mit definiertem Phosphorgehalt erforderlich ist, ist Ferrophosphor ungeeignet.For applications in which high-purity iron powder with a defined phosphorus content Ferrophosphorus is unsuitable.

In Bourcier et al., J. Vac. Sci. Technol. A 1986, 4, Seite 2943-48 ist die Herstellung von Eisen-Phosphor-Filmen durch Zersetzung von PH3 und Eisenpentacarbonyl beschrieben. In diesem als PECVD (plasma enhanced chemical vapor deposition) bekannten Verfahren wird aus einer Gasmischung, die die Komponenten verdünnt in einem Wasserstoff-Trägergasstrom enthält, in einer Glühentladung ein Plasma erzeugt, aus dem die Abscheidung der Filme auf einer beheizten Nickel-Substratoberfläche erfolgt. Die so hergestellten ultradünnen, amorphen Filme weisen einen Eisengehalt von 67 %, einen Sauerstoffgehalt von 2 % und einen Kohlenstoffgehalt von 10 % auf.In Bourcier et al., J. Vac. Sci. Technol. A 1986 , 4, page 2943-48 describes the production of iron-phosphor films by decomposing PH 3 and iron pentacarbonyl. In this known as PECVD (p lasma e nhanced c hemical v apor d eposition) process carrier gas stream, hydrogen plasma is from a gas mixture, which dilutes the components in a containing, in a glow discharge generated from the deposition of films on a heated Nickel substrate surface takes place. The ultrathin, amorphous films produced in this way have an iron content of 67%, an oxygen content of 2% and a carbon content of 10%.

GB-A-824 147 offenbart ein Verfahren zur Herstellung von phosphorhaltigem Eisen, bei dem Phosphortrichloriol als phosphorhaltige komponente mit Eisenpentacarbonyl umgesetzt wird.GB-A-824 147 discloses a method of manufacture of phosphorus-containing iron, in which phosphorus trichloriol as a phosphorus-containing component with iron pentacarbonyl is implemented.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von feinteiligem phosphorhaltigem Eisen mit einem in weiten Grenzen variierbaren Phosphorgehalt und einem geringen Anteil an Nebenbestandteilen bereitzustellen. Insbesondere lag der Erfindung die Aufgabe zugrunde, ein Verfahren zur Herstellung von feinteiligem phosphorhaltigem Eisen auf der Basis des Verfahrens zur Herstellung von Carbonyleisenpulver bereitzustellen.The invention has for its object a method for manufacturing of fine-particle phosphorus-containing iron with a wide range variable phosphorus content and a small proportion of secondary components provide. In particular, the invention was based on the object Process for the production of finely divided iron containing phosphorus on the To provide the basis of the process for the production of carbonyl iron powder.

Die Erfindung geht aus von bekannten Verfahren zur Herstellung von phosphorhaltigem Eisen aus einer phosphorhaltigen und einer eisenhaltigen Komponente. Das erfindungsgemäße Verfahren ist im Anspruch 1 gegeben.The invention is based on known processes for producing phosphorus-containing Iron from a phosphorus and an iron component. The method according to the invention is given in claim 1.

Geeignete Phosphorverbindungen sind Phosphane oder Alkylphosphane. Beispiele sind Phosphan (PH3), Diphosphan (P2H4), Methylphosphan, Dimethylphosphan und Trimethylphosphan. Bevorzugt wird PH3 verwendet.Suitable phosphorus compounds are phosphines or alkylphosphines. Examples are phosphine (PH 3 ), diphosphine (P 2 H 4 ), methylphosphine, dimethylphosphine and trimethylphosphine. PH 3 is preferably used.

Vorteilhaft an dem erfindungsgemäßen Verfahren ist, daß sich durch die Wahl der Gaszusammensetzung der Phosphorgehalt des feinteiligen phoshorhaltigen Eisenpulvers in weiten Grenzen variieren läßt. Grundsätzlich ist das Verhältnis von Eisenpentacarbonyl zu der Phosphorverbindung in der Gasmischung beliebig wählbar, wobei in der Regel - bezogen auf das Gewicht - Eisenpentacarbonyl im Überschuß verwendet wird. Vorzugsweise wird mit einem Überschuß an Eisenpentacarbonyl von mindestens 10:1, besonders bevorzugt 15:1, insbesondere mit einem Überschuß zwischen 15:1 und 300:1 gearbeitet.An advantage of the method according to the invention is that Choice of gas composition, the phosphorus content of the finely divided phosphorus-containing Iron powder can vary within wide limits. Basically it is Ratio of iron pentacarbonyl to the phosphorus compound in the gas mixture freely selectable, usually - based on the weight - Iron pentacarbonyl is used in excess. Preferably with an excess of iron pentacarbonyl of at least 10: 1, especially preferably 15: 1, in particular with an excess between 15: 1 and 300: 1 worked.

Das entstandene feinteilige phosphorhaltige Eisen kann einen Phosphorgehalt bis zu 50 Gew.-% aufweisen. Vorzugsweise liegt der Phosphorgehalt zwischen 0,1 und 20 Gew.-%. Der Phosphorgehalt kann nach bekannten Verfahren der Elementaranalyse, beispielsweise naßchemisch, durch Atomemissionsspektroskopie oder durch Röntgenmikrobereichsanalyse aus REM-Aufnahmen bestimmt werden.The resulting finely divided iron containing phosphorus can have a phosphorus content have up to 50 wt .-%. The phosphorus content is preferably between 0.1 and 20% by weight. The phosphorus content can be determined by known methods elemental analysis, for example wet chemical, by atomic emission spectroscopy or by X-ray micro-area analysis from SEM images be determined.

Die Umsetzung kann in einem beheizbaren Zersetzer, wie er beispielsweise für die Herstellung von Carbonyleisenpulver durch thermische Zersetzung von Eisenpentacarbonyl verwendet wird und in in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 14, Seite 599 bzw. in DE 3 428 121 oder DE 3 940 347 beschrieben ist, durchgeführt werden. Ein solcher Zersetzer umfaßt ein vorzugsweise vertikal angeordnetes Rohr aus einem hitzebeständigen Material wie Quarzglas oder V2A-Stahl, das von einer Heizeinrichtung, beispielsweise bestehend aus Heizbändern, Heizdrähten oder einem von einem Heizmedium durchströmten Heizmantel, umgeben ist. Bevorzugt ist die Heizeinrichtung zur Einstellung einer Zone niedriger Temperatur und einer Zone höherer Temperatur in mindestens 2 Segmente unterteilt. Die Gase werden vorgemischt und vorzugsweise von oben in das Zersetzerrohr eingeleitet, wobei die Gasmischung die Zone niedriger Temperatur zuerst passiert. Bevorzugt liegt die Temperatur des heißeren (unteren) Rohrabschnitts um mindestens 20°C über der Temperatur des kühleren Rohrabschnitts. Das so eingestellte Temperaturprofil begünstigt vermutlicht die Bildung des feinteiligen phosphorhaltigen Eisens durch die sich im Bereich des Temperaturgefälles ausbildende konvektive Gasströmung. Das entstandene feinteilige phosphorhaltige Eisen kann in einem Abscheider nach bekannten Verfahren durch Ausnutzung von Schwerkraft oder Zentrifugalkraft und/oder unter Verwendung von Filtereinrichtungen abgetrennt werden. Vorzugsweise ist die Masse der gebildeten Partikel so hoch, daß diese problemlos nach unten aus dem Zersetzer herausrieseln und in einem Vorlagegefäß aufgefangen werden können. Bei feineren Partikeln, die vom Gasstrom mitgerissen werden würden, kann eine Abtrennung durch ein- oder mehrmaliges Umlenken des Gasstroms im Abscheider und/oder Verwendung geeigneter Filter erreicht werden.The reaction can be carried out in a heatable decomposer, for example for the production of carbonyl iron powder by thermal decomposition of iron pentacarbonyl is used and in in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 14, page 599 or in DE 3 428 121 or DE 3 940 347 is carried out. On such a decomposer comprises a preferably vertically arranged tube a heat-resistant material such as quartz glass or V2A steel, made by a heating device, for example consisting of heating tapes, heating wires or a heating jacket through which a heating medium flows. The heating device for setting a zone is preferably lower Temperature and a zone of higher temperature in at least 2 segments divided. The gases are premixed and preferably from above into the Decomposition pipe initiated, the gas mixture entering the zone of low temperature happened first. The temperature of the hotter (lower) is preferably Pipe section at least 20 ° C above the temperature of the cooler pipe section. The temperature profile set in this way presumably favors the Formation of the finely divided phosphorus-containing iron due to the in the area convective gas flow forming the temperature gradient. The resulting finely divided phosphorus-containing iron can in a separator according to known Method using gravity or centrifugal force and / or be separated using filter devices. Preferably the mass of the particles formed is so high that it can easily re-adjust trickle out of the decomposer at the bottom and collected in a receptacle can be. For finer particles that are entrained by the gas flow would be a separation by single or multiple redirection the gas flow in the separator and / or use of suitable filters can be achieved.

Die Umsetzung wird bei Temperaturen oberhalb der Raumtemperatur durchgeführt. Die Temperatur liegt oberhalb 200°C, besonders bevorzugt zwischen 250°C und 375°C.The reaction is carried out at temperatures above room temperature. The temperature is above 200 ° C, especially preferably between 250 ° C and 375 ° C.

In einer bevorzugten Ausführungsform wird die Umsetzung in Gegenwart von Ammoniak, das vermutlich die Zersetzung von Eisenpentacarbonyl in Eisen und Kohlenmonoxid beschleunigt, durchgeführt. Vorzugsweise liegt der Anteil an Ammoniak in der Gasmischung zwischen 0,1 und 10 Vol-%.In a preferred embodiment, the reaction is in the presence of ammonia, which is believed to be the decomposition of iron pentacarbonyl in Accelerated iron and carbon monoxide, performed. Preferably, the Amount of ammonia in the gas mixture between 0.1 and 10 vol%.

Die Umsetzung wird vorzugsweise unter Ausschluß von atmosphärischem Sauerstoff durchgeführt, wobei in Gegenwart zusätzlicher Trägergase gearbeitet werden kann. Bevorzugt wird Kohlenmonoxid als zusätzlichem Trägergas verwendet. Der CO-Gehalt der Gasmischung liegt dabei vorzugsweise zwischen 10 und 90 %. Der Gesamtdruck bei der Umsetzung beträgt vorzugsweise zwischen 1 und 5 bar, besonders bevorzugt wird die Umsetzung bei Atmosphärendruck durchgeführt.The reaction is preferably carried out in the absence of atmospheric Oxygen carried out, working in the presence of additional carrier gases can be. Carbon monoxide is preferred as an additional Carrier gas used. The CO content of the gas mixture is preferably in this case between 10 and 90%. The total pressure during implementation is preferably between 1 and 5 bar, particularly preferred is the reaction carried out at atmospheric pressure.

Besonders vorteilhaft an dem erfindungsgemäßen Verfahren ist die hohe Reinheit des erhaltenen feinteiligen phosphorhaltigen Eisens, die auf die Verwendung der besonders reinen, gasförmigen Ausgangsstoffe zurückzuführen ist. So liegen im allgemeinen der Kohlenstoffgehalt unter 1 Gew.-%, der Stickstoffgehalt unter 1 Gew.-% und der Wasserstoffgehalt unter 0,5 Gew.-%.The high advantage of the process according to the invention is particularly advantageous Purity of the finely divided phosphorus-containing iron obtained on the Attributed to the use of particularly pure, gaseous starting materials is. In general, the carbon content is below 1% by weight, the nitrogen content below 1% by weight and the hydrogen content below 0.5 Wt .-%.

Bevorzugt weisen die erfindungsgemäß erhaltenen phosphorhaltigen Eisenpulver folgende Gehalte an Fremdelementen auf: Nickel < 100 ppm, Chrom < 150 ppm, Molybdän < 20 ppm, Arsen < 2 ppm, Blei < 10 ppm, Cadmium < 1 ppm, Kupfer < 5 ppm, Mangan < 10 ppm, Quecksilber < 1 ppm, Schwefel < 10 ppm, Silizium < 10 ppm, Zink < 10 ppm. Der Fremdelementgehalt kann mittels Atomabsorptions-Spektralanalyse bestimmt werden. Der geringe Fremdelementgehalt, der meist unterhalb der Nachweisgrenze der Atomabsorptions-Spektralanalyse liegt, unterscheidet das nach dem erfindungsgemäßen Verfahren hergestellte phosphorhaltige Eisen deutlich von nach bekannten Verfahren hergestelltem phosphorhaltigem Eisen.The phosphorus-containing iron powders obtained according to the invention preferably have the following levels of foreign elements: nickel <100 ppm, chromium <150 ppm, molybdenum <20 ppm, arsenic <2 ppm, lead <10 ppm, Cadmium <1 ppm, copper <5 ppm, manganese <10 ppm, mercury <1 ppm, sulfur <10 ppm, silicon <10 ppm, zinc <10 ppm. The foreign element content can be determined by means of atomic absorption spectral analysis become. The low foreign element content, which is usually below the Detection limit of the atomic absorption spectral analysis is different phosphorus-containing iron produced by the process according to the invention clearly of phosphorus-containing iron produced by known processes.

Weiterhin ist vorteilhaft, daß das phosphorhaltige Eisen in dem erfindungsgemäßen Verfahren in feinteiliger Form anfällt und insoweit eine mechanische Nachbehandlung, beispielsweise durch Mahlen, entfallen kann.It is also advantageous that the phosphorus-containing iron in the invention Process in finely divided form and thus a mechanical Aftertreatment, for example by grinding, can be omitted.

Bei der Umsetzung fällt das feinteilige phosphorhaltige Eisen entweder als im wesentlichen aus kugelförmigen Teilchen bestehendes Pulver oder als feine, polykristalline Fäden, sogenannten Whiskers, an.During the implementation, the fine-particle phosphorus-containing iron either falls as powder consisting essentially of spherical particles or as fine, polycrystalline threads, so-called whiskers.

Die erfindungsgemäßen phosphorhaltigen Eisenpulver bestehen im wesentlichen aus kugelförmigen Teilchen mit einem mittleren Teilchendurchmesser zwischen 0,3 und 20 µm, bevorzugt zwischen 1 und 10 µm. Mittlere Teilchendurchmesser können nach bekannten Verfahren fotographisch oder mit Streulichtmethoden, beispielsweise mit einem Laserstreulichtphotometer, bestimmt werden.The iron powders containing phosphorus according to the invention essentially consist from spherical particles with an average particle diameter between 0.3 and 20 µm, preferably between 1 and 10 µm. Average particle diameter can be photographically or with known methods Scattered light methods, for example with a laser scattered light photometer, be determined.

Die erfindungsgemäßen phosphorhaltigen Eisenwhiskers bestehen im wesentlichen aus fadenförmigen Agregaten von Kugeln mit einem Durchmesser der Kugeln zwischen 1 und 3 µm.The iron whiskers containing phosphorus according to the invention essentially exist from filiform aggregates of spheres with a diameter of Balls between 1 and 3 µm.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist, daß durch Wahl der Reaktionsparameter wie Druck, Temperatur und Durchströmgeschwindigkeit entweder Pulver oder Whiskers erhalten werden können, ferner der mittlere Teilchendurchmesser der Pulver durch Wahl dieser Parameter variiert werden kann.Another advantage of the method according to the invention is that by choice the reaction parameters such as pressure, temperature and flow rate either powder or whiskers can be obtained, furthermore the average particle diameter of the powder by choosing these parameters can be varied.

Die mechanischen Eigenschaften von Phosphor-Eisen-Legierungen werden insbesondere durch ihren Phosphorgehalt bestimmt. Die erfindungsgemäßen phosphorhaltigen Eisenpulver werden daher besonders vorteilhaft für Anwendungen, bei denen es auf die Einstellung bestimmter mechanischer Eigenschaften wie Härte oder Sprödigkeit ankommt, eingesetzt.The mechanical properties of phosphorus-iron alloys are determined in particular by their phosphorus content. The invention phosphorus-containing iron powders are therefore particularly advantageous for applications where it depends on the setting of certain mechanical properties how hardness or brittleness is used.

Bevorzugte Anwendungen des erfindungsgemäßen feinteiligen phosphorhaltigen Eisens liegen auf dem Gebiet der Pulvermetallurgie. Die Pulvermetallurgie ist ein Spezialgebiet der Werkstofferzeugung und -verarbeitung, bei dem pulverförmige Stoffe auf metallischer Basis durch Pressen und/oder Sintern zu Formkörpern verbunden werden. Bevorzugte Anwendungen sind beispielsweise das Formpressen und der Pulverspritzguß ("Metal Injection molding").Preferred applications of the finely divided phosphorus-containing invention Eisens are in the field of powder metallurgy. Powder metallurgy is a special field of material production and processing, in which Powdery materials on a metallic basis by pressing and / or sintering be connected to form bodies. Preferred applications are, for example compression molding and powder injection molding ("metal injection molding").

Das erfindungsgemäße feinteilige phosphorhaltige Eisen kann für sich allein oder gemischt mit anderen Metallpulvern - z.B. aus Nickel, Kobalt, Bronze - zur Herstellung von Eisenlegierungen eingesetzt werden.The fine-particle phosphorus-containing iron according to the invention can by itself or mixed with other metal powders - e.g. made of nickel, cobalt, bronze - be used to manufacture iron alloys.

Nach den obengenannten Verfahren kann das erfindungsgemäße feinteilige phosphorhaltige Eisen beispielsweise zum Einbetten von Industriediamanten in Schneide- und Schleifwerkzeugen sowie zur Herstellung von Metallkeramiken, sogenannten Cermets, verwendet werden.According to the above-mentioned method, the fine particle according to the invention phosphorus-containing iron, for example, for embedding industrial diamonds in cutting and grinding tools and for the production of metal ceramics, so-called cermets can be used.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert: The invention is illustrated by the following examples:

BEISPIELE 1 BIS 13EXAMPLES 1 TO 13

Die Apparatur zur thermischen Zersetzung von Eisenpentacarbonyl [Fe(CO)5] und Phosphan (PH3) besteht aus einem Zersetzerrohr von 1 m Länge und 20 cm Innendurchmesser aus V2A-Stahl. Das Zersetzerrohr wird mit Heizbändern beheizt, wobei im untersten Drittel des Rohres eine T2 eingestellt wird, die um mindestens 20°C höher liegt als die Temperatur T1 im oberen Teil des Rohres. Das flüssig vorgehaltene Fe(CO)5 wird in einem elektrisch beheizten Vorlagegefäß verdampft und der Dampf zusammen mit PH3 und CO (ca. 15 l/h) und NH3 (ca. 1 l/h) von oben in das Zersetzerrohr eingeleitet. Im Zersetzerrohr läuft die Bildung des phosphorhaltigen Eisenpulvers unter Freisetzung von CO und H2 ab. Das entstandene phosphorhaltige Eisenpulver rieselt nach unten aus dem Zersetzer heraus und wird in einem Glaskolben aufgefangen.
Zur Überprüfung des PH3-Gehaltes im Abgas wird das Abgas durch Quecksilber(II)-chlorid-Lösung geleitet und der gebildete Niederschlag auf Phosphor analysiert. Es wurden nur Spuren von Phosphor nachgewiesen, woraus auf einen vollständigen Umsatz des eingesetzten PH3 geschlossen werden kann. Die Bestimmung der Elementzusammensetzung erfolgt aus REM-Aufnahmen mittels Röntgenmikrobereichsanalyse.
Mittlere Teilchendurchmesser werden mit einem Laserstreulichtphotometer bestimmt.The apparatus for the thermal decomposition of iron pentacarbonyl [Fe (CO) 5 ] and phosphine (PH 3 ) consists of a decomposition tube of 1 m length and 20 cm inside diameter made of V2A steel. The decomposing tube is heated with heating tapes, a T 2 being set in the bottom third of the tube, which is at least 20 ° C. higher than the temperature T 1 in the upper part of the tube. The liquid Fe (CO) 5 is evaporated in an electrically heated storage vessel and the steam together with PH 3 and CO (approx. 15 l / h) and NH 3 (approx. 1 l / h) are introduced into the decomposition tube from above. The formation of the phosphorus-containing iron powder takes place in the decomposition tube with the release of CO and H 2 . The resulting phosphorus-containing iron powder trickles down out of the decomposer and is collected in a glass flask.
To check the PH 3 content in the exhaust gas, the exhaust gas is passed through mercury (II) chloride solution and the precipitate formed is analyzed for phosphorus. Only traces of phosphorus were detected, from which a complete conversion of the PH 3 used can be concluded. The element composition is determined from SEM images using X-ray micro-area analysis.
Average particle diameters are determined using a laser scattered light photometer.

BEISPIEL 14EXAMPLE 14

Die Darstellung erfolgte wie in den vorangegangenen Beispielen, doch wurde nicht in Gegenwart von Ammoniak gearbeitet.
Die Reaktionsprodukte und die Charakterisierung der Verfahrensprodukte sind der nachstehenden Tabelle zu entnehmen.

Figure 00090001
The presentation was as in the previous examples, but no work was carried out in the presence of ammonia.
The reaction products and the characterization of the process products are shown in the table below.
Figure 00090001

Claims (4)

  1. A process for preparing finely divided phosphorus- containing iron consisting essentially of spherical particles having a mean diameter of from 1 to 10 µm or of thread-like aggregates of spheres having a diameter of from 1 to 3 µm by reacting a phosphorus-containing component with an iron-containing component in the gas phase at above 200°C, wherein iron pentacarbonyl is reacted with a phosphine or alkylphosphine.
  2. A process as claimed in claim 1, wherein iron pentacarbonyl is reacted with phosphine.
  3. A process as claimed in claim 1 or 2, wherein the reaction is carried out in the presence of ammonia.
  4. Finely divided phosphorus-containing iron consisting essentially of spherical particles having a mean diameter of from 1 to 10 µm or of thread-like aggregates of spheres having a diameter of from 1 to 3 µm having the features:
    phosphorous content of from 0.1 to 50% by weight,
    carbon content below 1% by weight,
    nitrogen content below 1% by weight,
    hydrogen content below 0.5% by weight,
    total content of further extraneous elements below 0.1%, balance iron,
    able to be prepared by a process as claimed in any of claims 1 to 4.
EP98102811A 1997-02-19 1998-02-18 Fine iron powder containing phosphorus Expired - Lifetime EP0861699B1 (en)

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DE10013298C2 (en) * 2000-03-09 2003-10-30 Atotech Deutschland Gmbh Method for applying a metal layer on light metal surfaces and application of the method
US7410610B2 (en) * 2002-06-14 2008-08-12 General Electric Company Method for producing a titanium metallic composition having titanium boride particles dispersed therein
US7416697B2 (en) 2002-06-14 2008-08-26 General Electric Company Method for preparing a metallic article having an other additive constituent, without any melting
US6849229B2 (en) 2002-12-23 2005-02-01 General Electric Company Production of injection-molded metallic articles using chemically reduced nonmetallic precursor compounds
US7531021B2 (en) 2004-11-12 2009-05-12 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US7967891B2 (en) * 2006-06-01 2011-06-28 Inco Limited Method producing metal nanopowders by decompositon of metal carbonyl using an induction plasma torch
RU2458760C2 (en) * 2010-10-25 2012-08-20 Трофимов Сергей Иванович Method of producing iron powder that contains phosphorus
CN103386493A (en) * 2013-07-19 2013-11-13 江西悦安超细金属有限公司 Preparation method of carbonyl iron phosphate powder for diamond tool

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