EP2050528B1 - Atmosphere for metal atomization including gaseous hydride - Google Patents

Atmosphere for metal atomization including gaseous hydride Download PDF

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Publication number
EP2050528B1
EP2050528B1 EP07020458A EP07020458A EP2050528B1 EP 2050528 B1 EP2050528 B1 EP 2050528B1 EP 07020458 A EP07020458 A EP 07020458A EP 07020458 A EP07020458 A EP 07020458A EP 2050528 B1 EP2050528 B1 EP 2050528B1
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EP
European Patent Office
Prior art keywords
atmosphere
atomization
gaseous hydride
metal
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP07020458A
Other languages
German (de)
French (fr)
Other versions
EP2050528A1 (en
Inventor
Sören Wiberg
Johan Öhrling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Priority to EP07020458A priority Critical patent/EP2050528B1/en
Priority to AT07020458T priority patent/ATE537923T1/en
Priority to ES07020458T priority patent/ES2378260T3/en
Publication of EP2050528A1 publication Critical patent/EP2050528A1/en
Application granted granted Critical
Publication of EP2050528B1 publication Critical patent/EP2050528B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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

Definitions

  • the invention relates to a method for producing a metal powder by atomizing a molten metal by means of an atomization gas.
  • Metal atomization is a process for the production of fine metal powders.
  • the raw material is melted and then the liquid metal is broken into fine particles. This is achieved by atomizing a flow of the liquid metal by an atomization agent such as water or a gas.
  • the atomization agent strucks the liquid metal at a high velocity whereby the molten metal is disintegrated into fine droplets which solidify thereafter.
  • the fine metal particles absorb oxygen from the atomization agent which might react with alloying elements and might cause problems in the production of special alloyed metal powder.
  • an inert gas for example nitrogen or argon.
  • US 4,124,377 discloses a method for producing metal powder wherein the liquid metal is subjected to a reducing atomization agent such as hydrocarbon.
  • a reducing atomization agent such as hydrocarbon.
  • the actual pulverization process is performed in a closed chamber which is partially filled with a reducing liquid and is under pressure from a gaseous reducing agent.
  • DE 44 12 768 A1 discloses a method for atomization of a metallic melt.
  • the melt is atomized using a gas mixture comprising a carrier gas and a reactive gas, for example borane.
  • US 5, 147, 448 discloses techniques for producing fine metal powder including gas atomization.
  • Materials used to interact with the pulverized metal can include for example boron hydrides.
  • Gaseous hydrides such as silane are known to have a very high reactivity with oxygen containing substances or compounds.
  • silane or mono silane undergoes a spontaneous reaction with oxygen as well as with air: SiH 4 + O 2 ----> SiO 2 + 2 H 2 SiH 4 + 2 H 2 O ----> SiO 2 + 4 H 2
  • any oxygen remnants or any water vapour present reacts with the gaseous hydride.
  • the oxygen content in the atomization gas is extremely reduced and an atomization gas with an extreme low dew point and low partial pressure of oxygen is achieved.
  • the invention relates to the atomization of molten metal.
  • atomization in general means the disintegration of the molten metal by addition of a jet stream of an atomization agent. Since the invention is related to the use of a gaseous atomization agent in the following the term “atomization” shall mean the disintegration of molten metal by means of a high speed gas stream.
  • silanes or boranes are added to the atomization gas.
  • Silanes are chemical compounds of silicon and hydrogen.
  • the lowest silanes, mono silane with the chemical formula SiH 4 and di silane with the chemical formula Si 2 H 6 are gaseous and thus are particularly suitable for the invention.
  • Boranes are chemical compounds of boron and hydrogen.
  • the two smallest members of the borane group are mono borane or simply borane BH 3 and di borane B 2 H 6 . All these compounds are known to be very reactive with oxygen and air.
  • these boranes are also preferably used for reducing the oxygen content of the atomization gas.
  • the metal Prior to atomization the metal is held in the molten state. During that stage there is also a risk that the molten metal is oxidized by contact with the surrounding atmosphere.
  • the molten metal is preferably subjected to a particular process atmosphere with a low oxygen content.
  • the molten metal is then mixed with a high velocity stream of the atomization gas and sprayed in order to get fine metal droplets. It has also been found advantageous to spray the resulting metal droplets into a cooling atmosphere with reduced oxygen content.
  • the gaseous hydride is not only used to reduce the oxygen content of the atomization gas but also utilized to reduce the oxygen content of the process atmosphere and/or of the cooling atmosphere. Especially it is preferred to add a gaseous hydride to the atomization gas and to the process atmosphere and to the cooling atmosphere.
  • the amount of the gaseous and reactive hydride which is added to the atomization gas, the process atmosphere and/or the cooling atmosphere is between 0.00001 % and 2 %, preferably between 0.001% to 0,05%.
  • the amount of hydride is determined based on one or more of the following factors:
  • the invention it is possible to extremely decrease the oxygen and moisture level of the atomization gas, in the process atmosphere and/or in the cooling atmosphere. Thus, it is possible to atomize metals which could not have been treated in this way before. Further, the invention allows to produce very fine-grained metal powder even if the metal comprises easily oxidizing alloying elements.
  • the invention is useful for the atomization of all kind of metals.
  • preferred metals and metal powders to be used with the inventive method are iron, low alloyed steel, austenitic stainless steel, ferritic stainless steel and duplex stainless steel, copper and copper alloys, nickel and nickel alloys.
  • a little amount of silane is added to the atomization gas, to the process atmosphere and/or to the cooling atmosphere.
  • the atmosphere will preferably contain pure nitrogen with addition of silane.
  • the inventive atomization gas is either plain nitrogen, plain hydrogen, plain argon or a mixture of these gases blended with a gaseous hydride.
  • Preferred gases or gas mixtures are
  • the mixture of nitrogen and hydrogen or the mixture of argon and hydrogen are preferably produced by blending pure nitrogen with hydrogen or pure argon with hydrogen, respectively.
  • the inventive method is not only useful to decrease the oxygen and water vapour content of the atomization gas, of the process atmosphere and/or of the cooling atmosphere. It can also be used as a reducing agent to react with other impurities present in the atomization gas, of the process atmosphere and/or of the cooling atmosphere, for example organic compounds.

Landscapes

  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention relates to a method for producing a metal powder by atomizing a molten metal by means of an atomization gas wherein said atomization gas, which is based e.g. on nitrogen, comprises a gaseous hydride, e.g. silane or borane.

Description

  • The invention relates to a method for producing a metal powder by atomizing a molten metal by means of an atomization gas.
  • Metal atomization is a process for the production of fine metal powders. The raw material is melted and then the liquid metal is broken into fine particles. This is achieved by atomizing a flow of the liquid metal by an atomization agent such as water or a gas. The atomization agent strucks the liquid metal at a high velocity whereby the molten metal is disintegrated into fine droplets which solidify thereafter.
  • During the production process the fine metal particles absorb oxygen from the atomization agent which might react with alloying elements and might cause problems in the production of special alloyed metal powder. Thus, instead of using water or compressed air as atomization agent it is already known to atomize the molten metal with an inert gas, for example nitrogen or argon.
  • US 4,124,377 discloses a method for producing metal powder wherein the liquid metal is subjected to a reducing atomization agent such as hydrocarbon. In order to protect the powder against oxidation, the actual pulverization process is performed in a closed chamber which is partially filled with a reducing liquid and is under pressure from a gaseous reducing agent.
  • DE 44 12 768 A1 discloses a method for atomization of a metallic melt. The melt is atomized using a gas mixture comprising a carrier gas and a reactive gas, for example borane.
  • US 5, 147, 448 discloses techniques for producing fine metal powder including gas atomization. Materials used to interact with the pulverized metal can include for example boron hydrides.
  • It is an object of the present invention to provide a method for atomization of metal wherein oxidation of the produced metal powder is avoided or at least significantly reduced.
  • This object is achieved by a method according to claim 1.
  • Gaseous hydrides such as silane are known to have a very high reactivity with oxygen containing substances or compounds. For example, at room temperature silane or mono silane undergoes a spontaneous reaction with oxygen as well as with air:

            SiH4 + O2 ----> SiO2 + 2 H2

            SiH4 + 2 H2O ----> SiO2 + 4 H2

  • By the inventive addition of a gaseous hydride to the atomization gas any oxygen remnants or any water vapour present reacts with the gaseous hydride. Thus, the oxygen content in the atomization gas is extremely reduced and an atomization gas with an extreme low dew point and low partial pressure of oxygen is achieved.
  • The invention relates to the atomization of molten metal. The term "atomization" in general means the disintegration of the molten metal by addition of a jet stream of an atomization agent. Since the invention is related to the use of a gaseous atomization agent in the following the term "atomization" shall mean the disintegration of molten metal by means of a high speed gas stream.
  • Preferably silanes or boranes are added to the atomization gas. Silanes are chemical compounds of silicon and hydrogen. The lowest silanes, mono silane with the chemical formula SiH4 and di silane with the chemical formula Si2H6, are gaseous and thus are particularly suitable for the invention.
  • Boranes are chemical compounds of boron and hydrogen. The two smallest members of the borane group are mono borane or simply borane BH3 and di borane B2H6. All these compounds are known to be very reactive with oxygen and air. Thus, these boranes are also preferably used for reducing the oxygen content of the atomization gas.
  • Prior to atomization the metal is held in the molten state. During that stage there is also a risk that the molten metal is oxidized by contact with the surrounding atmosphere. Thus the molten metal is preferably subjected to a particular process atmosphere with a low oxygen content.
  • The molten metal is then mixed with a high velocity stream of the atomization gas and sprayed in order to get fine metal droplets. It has also been found advantageous to spray the resulting metal droplets into a cooling atmosphere with reduced oxygen content.
  • Thus, according to a preferred embodiment of the invention the gaseous hydride is not only used to reduce the oxygen content of the atomization gas but also utilized to reduce the oxygen content of the process atmosphere and/or of the cooling atmosphere. Especially it is preferred to add a gaseous hydride to the atomization gas and to the process atmosphere and to the cooling atmosphere.
  • The amount of the gaseous and reactive hydride which is added to the atomization gas, the process atmosphere and/or the cooling atmosphere is between 0.00001 % and 2 %, preferably between 0.001% to 0,05%. The amount of hydride is determined based on one or more of the following factors:
    • quality (especially oxygen content) of the atomization gas prior to the addition of the hydride,
    • quality (especially oxygen content) of the process atmosphere prior to the addition of the hydride,
    • quality (especially oxygen content) of the cooling atmosphere prior to the addition of the hydride,
    • required level of oxygen and water in the atomization gas,
    • required level of oxygen and water in the process atmosphere,
    • required level of oxygen and water in the cooling atmosphere,
    • type of metal and alloying elements which shall be atomized ,
    • grain size of the metal powder product,
    • desired quality of the metal powder product.
  • According to the invention it is possible to extremely decrease the oxygen and moisture level of the atomization gas, in the process atmosphere and/or in the cooling atmosphere. Thus, it is possible to atomize metals which could not have been treated in this way before. Further, the invention allows to produce very fine-grained metal powder even if the metal comprises easily oxidizing alloying elements.
  • In general, the invention is useful for the atomization of all kind of metals. Examples for preferred metals and metal powders to be used with the inventive method are iron, low alloyed steel, austenitic stainless steel, ferritic stainless steel and duplex stainless steel, copper and copper alloys, nickel and nickel alloys.
  • According to a preferred embodiment of the invention a little amount of silane is added to the atomization gas, to the process atmosphere and/or to the cooling atmosphere. The atmosphere will preferably contain pure nitrogen with addition of silane.
  • In general, the inventive atomization gas is either plain nitrogen, plain hydrogen, plain argon or a mixture of these gases blended with a gaseous hydride. Preferred gases or gas mixtures are
    • plain nitrogen,
    • a mixture of an inert gas and hydrogen,
    • a mixture of nitrogen and hydrogen,
    • a mixture of argon and hydrogen,
    • a mixture of nitrogen, argon and hydrogen,
    wherein to each of the above atmospheres a gaseous hydride, especially silane, is added.
  • The same applies to the process atmosphere and to the cooling atmosphere. It is also preferred to use an inert gas blended with a gaseous hydride, especially with silane. Preferred mixtures are
    • plain nitrogen plus a gaseous hydride,
    • a mixture of an inert gas and hydrogen plus a gaseous hydride,
    • a mixture of nitrogen and hydrogen plus a gaseous hydride,
    • a mixture of argon and hydrogen plus a gaseous hydride,
    • a mixture of nitrogen, argon and hydrogen plus a gaseous hydride.
  • The mixture of nitrogen and hydrogen or the mixture of argon and hydrogen are preferably produced by blending pure nitrogen with hydrogen or pure argon with hydrogen, respectively.
  • The inventive method is not only useful to decrease the oxygen and water vapour content of the atomization gas, of the process atmosphere and/or of the cooling atmosphere. It can also be used as a reducing agent to react with other impurities present in the atomization gas, of the process atmosphere and/or of the cooling atmosphere, for example organic compounds.

Claims (4)

  1. Method for producing a metal powder by atomizing a molten metal by means of an atomization gas, characterized in that said atomization gas consists of
    - nitrogen and a gaseous hydride or of
    - argon, hydrogen and a gaseous hydride or of
    - an inert gas and hydrogen and a gaseous hydride or of
    - a mixture of nitrogen, argon, hydrogen and a gaseous hydride,
    wherein the concentration of said gaseous hydride in said atomization gas is between 0.00001 % and 2 %, preferably between 0.001% to 0,1%.
  2. Method according to claim 1 characterized in that a process atmosphere is provided above said molten metal and wherein said process atmosphere comprises a gaseous hydride.
  3. Method according to any of claims 1 or 2 characterized in that after atomizing said molten metal the resulting metal powder is subjected to a cooling atmosphere comprising a gaseous hydride.
  4. Method according to any of claims 1 to 3 characterized in that said atomization gas, said process atmosphere and/or said cooling atmosphere comprise silane or borane.
EP07020458A 2007-10-18 2007-10-18 Atmosphere for metal atomization including gaseous hydride Not-in-force EP2050528B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP07020458A EP2050528B1 (en) 2007-10-18 2007-10-18 Atmosphere for metal atomization including gaseous hydride
AT07020458T ATE537923T1 (en) 2007-10-18 2007-10-18 ATMOSPHERE CONTAINING GASEOUS HYDRIDE FOR METAL ATOMIZATION
ES07020458T ES2378260T3 (en) 2007-10-18 2007-10-18 Process atmospheres for metal atomization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07020458A EP2050528B1 (en) 2007-10-18 2007-10-18 Atmosphere for metal atomization including gaseous hydride

Publications (2)

Publication Number Publication Date
EP2050528A1 EP2050528A1 (en) 2009-04-22
EP2050528B1 true EP2050528B1 (en) 2011-12-21

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EP07020458A Not-in-force EP2050528B1 (en) 2007-10-18 2007-10-18 Atmosphere for metal atomization including gaseous hydride

Country Status (3)

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EP (1) EP2050528B1 (en)
AT (1) ATE537923T1 (en)
ES (1) ES2378260T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3530385A1 (en) 2018-02-26 2019-08-28 Linde Aktiengesellschaft Method for the production of metallic powders

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3290134A1 (en) 2016-09-01 2018-03-07 Linde Aktiengesellschaft Method for additive manufacturing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124377A (en) 1977-07-20 1978-11-07 Rutger Larson Konsult Ab Method and apparatus for producing atomized metal powder
US5147448A (en) 1990-10-01 1992-09-15 Nuclear Metals, Inc. Techniques for producing fine metal powder
US5368657A (en) 1993-04-13 1994-11-29 Iowa State University Research Foundation, Inc. Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions
US20040065171A1 (en) * 2002-10-02 2004-04-08 Hearley Andrew K. Soild-state hydrogen storage systems

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3530385A1 (en) 2018-02-26 2019-08-28 Linde Aktiengesellschaft Method for the production of metallic powders
WO2019161971A1 (en) 2018-02-26 2019-08-29 Linde Aktiengesellschaft Method for the production of metallic powders

Also Published As

Publication number Publication date
ES2378260T3 (en) 2012-04-10
ATE537923T1 (en) 2012-01-15
EP2050528A1 (en) 2009-04-22

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