EP0134808A4 - Method for making ultrafine metal powder. - Google Patents
Method for making ultrafine metal powder.Info
- Publication number
- EP0134808A4 EP0134808A4 EP19840900776 EP84900776A EP0134808A4 EP 0134808 A4 EP0134808 A4 EP 0134808A4 EP 19840900776 EP19840900776 EP 19840900776 EP 84900776 A EP84900776 A EP 84900776A EP 0134808 A4 EP0134808 A4 EP 0134808A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- fine powder
- particles
- stream
- powder according
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
- B22F9/10—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 using centrifugal force
Definitions
- the present invention relates to a process for making rapidly cooled fine metal powders.
- U.S. patent 3,646,177 to Thompson discloses a method for producing powdered metals and alloys that are free from oxidation by a process which involves atomizing molten metal with a fluid jet to form discrete particles of the molten metal.
- the jet is directed into a reservoir of an inert cryogenic liquid to solidify the particles and prevent oxidation during cooling.
- U.S. patent 4,069,045 to Lundgren describes a process wherein a jet of molten metal is impinged against a rotating flat disc. Relatively thin, brittle, easily shattered, and essentially dentrite free metal flakes are obtained. These flakes are also described in U.S. patent 4,063,942 to Lundgren.
- U.S. patent 4,221,587 to Ray relates to a method of making powder by impinging a jet of molten alloy at an acute angle against the inner .surface of a rotating cylindrical chill body.
- the impinging molten metal breaks into a stream of discrete droplets which bounce off the surface and move in the direction of the chill surface.
- the droplets are solidified at a rapid rate.
- the glassy metal powder particles ... have relatively sharp notched edges which enable the particles to interlock during compaction.”
- the particle size of the powder is such that 90% of the particles have a particle size range between about 25 and 300 microns.
- the particle size of the powder ranges between 100 and 1000 microns.
- Herbert Herman and Hareesh Bhat in an article entitled “Metastable Phases Produced by Plasma Spraying” appearing in the proceedings of a symposium sponsored by the TMS-AIME alloy Phases Committee at the Fall meeting of the Metallurgical Society of AIME, Pittsburgh, Pennsylvania, October 5-9, 1980 describes the high velocity deposition of plasma-melting particles on a substrate.
- the article indicates that good physical and thermal contact should exist between the solidifying liquid and substrate. Liquid spreading occurs away from the impact point.
- the particles have a flat surface adjacent the substrate with a central raised core region and a circular rim area.
- Figure 1 is a schematic drawing of a device including a plasma spray apparatus and drum.
- Figure 2 is a schematic drawing of a device including a plasma spray apparatus, substrate and gas discharge device.
- Figure 3 is a schematic drawing of plasma spray apparatus, endless belt, and discharge device for substrate material.
- Atomized metal or metal alloy powders in the one to ten micrometer size range are desirable for many applications such as electrostatic copying and for rapid
- a fine powder wherein a substantial portion of the particles have smoothly curvilinear surfaces and an average particle size less than about ten micrometers. Also, in accordance with the present invention, there is provided a process for making very fine metal powder. A high velocity stream of molten metal droplets is directed toward a repellent surface. The molten droplets are impacted against the surface to fragment the droplets and form still molten fragmented portions which are rapidly cooled to form a fine metal powder.
- the resulting powder comprises particles less than about ten micrometers with curvilinear surface.
- Inorganic materials for thermal spraying include ceramics and cermets.
- the preferred powders are metals and metal alloys.
- Low melting metals or alloys may include zinc, lead, silver or gold. Higher melting point metals and alloys typically contain copper, cobalt, iron and nickel may be used.
- the refractory metals and alloys which typically have melting points in excess of 1800 degrees ⁇ entirade are of particular interest.
- the refractory type metals include molybdenum, niobium, tungsten, tantalum, chromium alloys and mixtures thereof.
- the term- etals include elemental metals, alloys, pure or mixed oxides, borides, carbides and nitrides of metal with or without additives.
- the powders of the present invention are produced by rapid cooling, at least some of the powders contain particles having amorphous phases or metastable crystal structures.
- Metal alloys which are most easily obtained in the amorphous state by rapid quenching or by deposition techniques are mixtures of transition metals. The cooling rate necessary to achieve the amorphous state depends on the composition of the alloys.
- the amorphous and crystalline state are distinguished most readily by differences in X-ray diffraction measurement. Diffraction patterns of an amorphous substance reveal a broad halo similar to a liquid. Crystalline materials produce a line or broadened line diffraction pattern.
- the amorphous alloys provided by the present invention appear to be liquid when studied from x-ray diffraction patterns, but the alloy is solid when studied in terms of hardness and viscosity.
- An amorphous alloy structure is inherently metastable, i.e., the state is non-equilibrium. Since the atoms of the amorphous structure are not arranged in a periodic array, there is at any temperature a tendency of the amorphous structure to transform toward the crystalline structure of' the equilibrium state through diffusion or segregation of components of the alloy.
- the rapidly cooled powder particles of the present invention preferably have a particle size distribution wherein at least about 80 percent of the particles have an average particle size less than about 10 microns. Depending on the composition and exact conditions of powder formation, even smaller particle size distributions wherein at least 90 percent of the particles have an average particle size less than about 10 microns may be formed. Another particle distribution includes greater than about 80 percent of the particles having average particle size greater than about 0.5 and less than about 8 microns.
- the particles of the present invention are preferably cooled from ultrafine portions of molten materials to give a characteristic curvilinear surface to the particles. Due to surface tension, airborn molten material tends to contract until the smallest surface area consistent with its volume is occupied. Due to the repellent nature of the repellent surface droplet formation is favored. The tendency of the molten material is to form spheres. If the rapidly cooled particles solidify prior to assuming the shape of a sphere or molten particles collide during cooling, the molten portions may form elliptically shaped or elongated particles with rounded ends.
- the powders of the present invention differ from milled or fractured powders which are characterized by an irregularly shaped outline which may have sharp or rough edges.
- the particles of the present invention exhibit BET diameters from about 1/2 micrometers to about 10 micrometers.
- a scanning Election Micrograph (SEM) photo of molybdenum powder of -the present invention has particles which have substantially smoothly curvilinear surfaces.
- the particles appear as small blobs or globs which are spheroidally and ovoidally shaped with arcuate and curved surfaces.
- the particles comprise cells of from about 0.01 to about 0.1 micrometers which are indicative of rapid cooling.
- a powder is fed through a thermal spray apparatus. Feed
- O PI powder is entrained in a carrier gas and then fed through a high temperature reactor.
- the temperature in the reactor is preferably above the melting point of the highest melting component of the metal powder and even more preferably above the vaporization point of the lowest vaporizing component of the material to enable a relatively short residence time in the reaction zone.
- the stream of dispersed entrained molten metal droplets may be produced by plasma-jet torch or gun apparatus of conventional nature.
- Typical plasma jet apparatus is of the resistance arc or induction type.
- a source of metal powder is connected to a source of propellant gas.
- a means is provided to mix the gas with the powder and propel the gas with entrained powder through a conduit communicating with a nozzle passage of the plasma spray apparatus.
- the entrained powder may be fed into a vortex chamber which communicates with and is coaxial with the nozzle passage which is bored centrally through the nozzle.
- an electric arc is maintained between an interior wall of the nozzle passage and an electrode present in the passage.
- the electrode has a diameter smaller than the nozzle passage with which it is coaxial to so that the gas is discharged from the nozzle in the form of a plasma jet.
- the current source is normally a DC source adapted to deliver very large currents at relatively low voltages.
- torch temperatures can range from 150 degrees centigrade up to about 15,000 degrees centigrade.
- the apparatus generally must be adjusted in accordance with the melting point of the powders being sprayed and the gas employed.
- the electrode may be retracted within the nozzle when lower melting powders are utilized with an inert gas such as nitrogen while the electrode may be more fully extended within the nozzle when higher melting powders are utilized with an inert gas such as argon.
- metal powder entrained in an inert gas is passed at a high velocity through a strong magnetic field so as to cause a voltage to be generated in the gas.
- the current source is adapted to deliver very high currents, on the order of 10,000 amperes, although the voltage may be relatively low such as 10 volts. Such currents are required to generate a very strong direct magnetic field and create a plasma.
- Such plasma devices may include additional means for aiding in the initiation of a plasma generation, a cooling means for the torch in the form of annular chamber around the nozzle.
- a gas which is ionized in the torch regains its heat of ionization on exiting the nozzle to create a highly intense flame.
- the flow of gas through the plasma " spray apparatus is effected at speeds at least approaching the speed of sound.
- the typical torch comprises a conduit means having a convergent portion which converges in a downstream direction to a throat. The convergent portion communicates with an adjacent outlet opening so that the discharge of plasma is effected out the outlet opening.
- torches may be used such as an oxy-acetylene type having high pressure fuel gas flowing ' through the nozzle.
- the powder may be introduced into the gas by an aspirating effect.
- the fuel is ignited at the nozzle outlet to provide a high temperature flame.
- the powders utilized for the torch should be uniform in size, and composition and relatively free flowing. Flowability is desirable to aid in the transportation and injection of the powder into the plasma flame. In general, fine powders (less
- OMPI than 40-micrometers average diameter do_.not exhibit good flow characteristics.
- a narrow size distribution is disirable because, under set flame conditions, the largest particles may not melt completely, and the smallest particles may be heated to the vaporization point. Incomplete melting is a detriment to the product uniformity, whereas vaporization and decomposition decreases process efficiency.
- the size ranges for plasma feed powders are such that 80 percent of the particles fall within a 30 micrometer diameter range with the range of substantially all the particles within a 60 micrometer range.
- U.S. Patent 3,909,241 to Cheney et al describes a process for preparing smooth, substantially spherical particles having an apparent density of at least 40 percent of the theoretical density of the material.
- metals which typically will not alloy in a melt may be intimately mixed in non-equilibrium phases to form a uniform powder composition.
- OMPI mcrease the droplet size. It is generally desriable that the stream flow in a radial direction toward the repellent surface if the surface is curved, and in a normal direction, if the surface is flat.
- the repellent surface is preferably a surface that is not weted by the molten material so as to increase the propensity of the material to form droplets on the surface.
- the wettability and relative surface energy of molten metal and a surface can be determined by measuring the contact angle between the liquid phase of the molten metal and the surface through the liquid phase. To favor droplet formation it is preferably to have contact angles greater than about ninety degrees.
- Typical surfaces may include ceramics such as alumina, silicon nitride, quartz; metal surfaces such as aluminum, copper, and inert solids which may be liquid or solid at room temperatures such as dry ice (CO2) or normal ice (H2O).
- the surfaces are preferably smooth.
- Molten droplets which impact the repellent surface are fragmented to form molten fragmented portions which are typically at least about one third the volume of the original droplet. After impact, the molten fragmented portions solidify to form the powder of the present invention which has substantially smoothly curvilinear surfaces.
- the molten fragmented portions may be cooled by contact with the repellent surface or by an atmosphere near the repellent surface.
- the cooling medium is preferably below the solidification temperature of the molten material.
- the fragmented particles may solidify after bouncing or rebounding off the surface.
- the repellent surface is the primary cooling medium, the major quenching may occur on or closely adjacent the surface.
- -li ⁇ lt is theorized that the particles tend toward sphericity due to the fact that molten fragments on the surface tend toward sphericity due to the repellent nature of the surface and rebounding molten fragments 5 tend toward sphericity due to the tendency to contract to the smallest surface area consistent with volume. It is believed that the high velocity tends to promote fragmentation of the particles. As droplets impact the surface, the component of velocity in the direction of 10 flight is immediately changed to a velocity component in a direction which is parallel to or at a slight angle to the surface. This force tends to promote fragmentation of the droplets.
- the rebounding fragmented 15 molten portions and solidified particles have a component of velocity in a given direction normal to the stream direction so as to remove fragmented portions from the path of oncoming droplets. If the nozzle is stationary with respect to the repellent surface, this 20 may be accomplished by passing an inert gas over the surface at a velocity sufficient to remove fragmented portions. The nozzle or the surface may also be moved relative to each other so as to remove fragmented portions from the oncoming stream of entrained 25 particles. To prevent impingement of droplets on fragmented portions, it is desirable that the previously fragmented droplets be passed out of the range of the oncoming droplets.
- FIG. 1 describes an apparatus for carrying out 3.0 the method fo the present invention.
- the gun 15 includes a nozzle radially directed at repellent surface 17 which is in the form of a drum.
- a source of high pressure gas 19 communicates with a powder source 21 for 5 entraining metal powder.
- the entrained powder is fed to nozzle 15.
- a source of D.C. powder 23 is electrically connected between the nozzle 15 and the elements 23 for forming plasma 25.
- fragmented portions are collected in a container 27.
- the drum is rotated so as to impart a tangential component of velocity to rebounding particles and remove the fragmented portions 31 from the path of the oncoming entrained droplets.
- Figure 2 illustrates another embodiment of the present invention where a nozzle 51 directs a plasma stream 53 against a rotating disc repellent surface 55. Another nozzle 57 is directed at the location of impact so as to direct a stream of inert gas 61 at rebounding fragmented portions 65 which are propelled toward container 59 where collected.
- Figure 3 illustrates another embodiment where plasma 70 from nozzle 71 is directed against a moving bed of repellent material 75 such as dry ice.
- the material 75 is deposited from hopper 77 at one end of the moving endless belt 79.
- the plasma 70 is directed at the moving bed so as to form fragmented portions 85 which are collected in container 81 at the other end of the endless belt 79.
- the velocity of the molten droplets in the respective plasma streams 25, 53, 70 is sufficient so that upon impacting respective repellent surfaces 17, 55 and 75 the droplets form fragmented portions.
- the surfaces 17, 55 and 75 are sufficiently repellent so as to favor droplet formation.
- Droplets of higher viscosities may require higher velocities for fragmenting droplets.
- a turbulent gaseous medium adjacent repellent surface may aid the solidification of rebounding particles.
- a turbulent gaseous medium or permitting the rebounding fragmented portions to fall away from the surface under the influence of gravity may enhance the solidification of the fragmented portions away from the surface and thus permit the utilization of less repellent surfaces.
- the use of a vacuum and permitting fragmented molten portions to fall back onto the repellent surface may enhance the solidification of the fragmented portions on the surface. In this later case, a highly repellent surface may be desirable.
- a Baystate, PG120-4, plasma gun is mounted in a chamber about 4 to about 6 inches from a block of dry ice.
- Agglomerated molybdenum powder (99.9 percent molybdenum) having a size distribution of about 56 percent -270 + 325 and about 44 percent -325 mesh is fed to the gun at the rate of 8.85 pounds per hour entrained in argon at about 10 cubic feet per hour.
- the argon plasma gas is fed to the torch at the rate of about 60 cubic feet per hour.
- the torch power is about 30 volts at 600 amperes.
- the chamber has a nitrogen atmosphere.
- the powder is sprayed in a normal direction onto a block of dry ice as the nozzle is moved back and forth over the block.
- a Scanning Electron Micrograph indicates that about 90 percent of the particles appear to be less than about 10 micrometers. At least a portion of the particles appear to have a cellular structure with the cells being from about 0.01 to 0.1 micrometers in size. The particles have smooth curvilinear surfaces tending toward sphericity. The particles .which are most rapidly cooled appear to have amorphous properties.
- EXAMPLE 2 In a manner similar to example 1, copper powder having a starting size of about 30 to 40 micrometers is reduced to copper particles having a particle size of about 1 to about 10 micrometers. The starting powder has a size distribution of 100 percent less than 270 mesh.
- the apparatus used is as describe'd in Example 1 except the powder feed rate is 5 7 pounds per hour, plasma gas feed rate is 60 cubic feet per hour, and about 405 grams of the powder is collected.
- the final powder exhibits the curvilinear structure similar to the powder structure as of Example 1.
- EXAMPLE 3 In a manner similar to Example 2, a powder consisting of nickel, chromium, and boron is plasma sprayed. The resulting powder which tends toward sphericity has an amorphous metastable structure.
- EXAMPLE 4 In a manner similar to Example 1, the dry ice bed is replaced with a ceramic substrate comprising quartz which has a high thermal shock resistance. The substrate surface is smooth and the cooling gas of nitrogen is directed at the surface in the impact area in a direction tangential to the plasma stream.
- Rebounding fragmented particles which are collected exhibit the spherical powder shape and have an average particle size less than about 10 micrometers.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US46070983A | 1983-01-24 | 1983-01-24 | |
US460709 | 1983-01-24 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0134808A1 EP0134808A1 (en) | 1985-03-27 |
EP0134808A4 true EP0134808A4 (en) | 1985-07-01 |
EP0134808B1 EP0134808B1 (en) | 1990-09-12 |
Family
ID=23829772
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84900776A Expired - Lifetime EP0134808B1 (en) | 1983-01-24 | 1984-01-06 | Method for making ultrafine metal powder |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0134808B1 (en) |
JP (1) | JPS60500872A (en) |
CA (1) | CA1236711A (en) |
DE (1) | DE3483189D1 (en) |
WO (1) | WO1984002864A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4783214A (en) * | 1988-02-29 | 1988-11-08 | Gte Products Corporation | Low oxygen content fine shperical particles and process for producing same by fluid energy milling and high temperature processing |
US5294242A (en) * | 1991-09-30 | 1994-03-15 | Air Products And Chemicals | Method for making metal powders |
WO2002047856A2 (en) * | 2000-12-15 | 2002-06-20 | Omg Americas, Inc. | Irregular shaped copper particles and methods of use |
DE602006007780D1 (en) * | 2005-10-21 | 2009-08-27 | Sulzer Metco Us Inc | Process for the production of highly pure flowable metal oxide powder by plasma melting |
KR101134501B1 (en) | 2009-12-07 | 2012-04-13 | 주식회사 풍산 | method for manufacture of high purity copper powder use of plasma |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3829538A (en) * | 1972-10-03 | 1974-08-13 | Special Metals Corp | Control method and apparatus for the production of powder metal |
US3974245A (en) * | 1973-12-17 | 1976-08-10 | Gte Sylvania Incorporated | Process for producing free flowing powder and product |
DE2528999C2 (en) * | 1975-06-28 | 1984-08-23 | Leybold-Heraeus GmbH, 5000 Köln | Process and device for the production of high-purity metal powder by means of electron beam heating |
US4264641A (en) * | 1977-03-17 | 1981-04-28 | Phrasor Technology Inc. | Electrohydrodynamic spraying to produce ultrafine particles |
DE2743090C3 (en) * | 1977-09-24 | 1980-04-30 | Battelle-Institut E.V., 6000 Frankfurt | Device for the production of film-shaped granulates from metallic melts |
US4408971A (en) * | 1978-03-27 | 1983-10-11 | Karinsky Viktor Nikolaevich | Granulation apparatus |
US4221587A (en) * | 1979-03-23 | 1980-09-09 | Allied Chemical Corporation | Method for making metallic glass powder |
US4326841A (en) * | 1979-03-23 | 1982-04-27 | Allied Chemical Corporation | Apparatus for making metallic glass powder |
US4376740A (en) * | 1981-01-05 | 1983-03-15 | National Research Institute For Metals | Process for production fine metal particles |
US4390368A (en) * | 1981-04-01 | 1983-06-28 | Gte Products Corporation | Flame spray powder |
US4374075A (en) * | 1981-06-17 | 1983-02-15 | Crucible Inc. | Method for the plasma-arc production of metal powder |
US4435342A (en) * | 1981-11-04 | 1984-03-06 | Wentzell Jospeh M | Methods for producing very fine particle size metal powders |
US4395279A (en) * | 1981-11-27 | 1983-07-26 | Gte Products Corporation | Plasma spray powder |
US4419060A (en) * | 1983-03-14 | 1983-12-06 | Dow Corning Corporation | Apparatus for rapidly freezing molten metals and metalloids in particulate form |
-
1984
- 1984-01-06 EP EP84900776A patent/EP0134808B1/en not_active Expired - Lifetime
- 1984-01-06 DE DE8484900776T patent/DE3483189D1/en not_active Expired - Fee Related
- 1984-01-06 JP JP50082184A patent/JPS60500872A/en active Pending
- 1984-01-06 WO PCT/US1984/000019 patent/WO1984002864A1/en active IP Right Grant
- 1984-01-23 CA CA000445826A patent/CA1236711A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
See references of WO8402864A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE3483189D1 (en) | 1990-10-18 |
CA1236711A (en) | 1988-05-17 |
EP0134808A1 (en) | 1985-03-27 |
WO1984002864A1 (en) | 1984-08-02 |
EP0134808B1 (en) | 1990-09-12 |
JPS60500872A (en) | 1985-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4592781A (en) | Method for making ultrafine metal powder | |
US4613371A (en) | Method for making ultrafine metal powder | |
US4687510A (en) | Method for making ultrafine metal powder | |
US5707419A (en) | Method of production of metal and ceramic powders by plasma atomization | |
US6398125B1 (en) | Process and apparatus for the production of nanometer-sized powders | |
US4731111A (en) | Hydrometallurical process for producing finely divided spherical refractory metal based powders | |
US6444009B1 (en) | Method for producing environmentally stable reactive alloy powders | |
US4802915A (en) | Process for producing finely divided spherical metal powders containing an iron group metal and a readily oxidizable metal | |
US4772315A (en) | Hydrometallurgical process for producing finely divided spherical maraging steel powders containing readily oxidizable alloying elements | |
JPS5835563B2 (en) | Manufacturing method and equipment for glassy metal powder | |
US4778517A (en) | Hydrometallurgical process for producing finely divided copper and copper alloy powders | |
US20200180034A1 (en) | Method for cost-effective production of ultrafine spherical powders at large scale using thruster-assisted plasma atomization | |
US4787934A (en) | Hydrometallurgical process for producing spherical maraging steel powders utilizing spherical powder and elemental oxidizable species | |
US5114471A (en) | Hydrometallurgical process for producing finely divided spherical maraging steel powders | |
CN111470481B (en) | Method for preparing high-purity aluminum nitride spherical powder by plasma reaction atomization | |
US4502885A (en) | Method for making metal powder | |
US4859237A (en) | Hydrometallurgical process for producing spherical maraging steel powders with readily oxidizable alloying elements | |
KR20040067608A (en) | Metal powder and the manufacturing method | |
EP0134808B1 (en) | Method for making ultrafine metal powder | |
CA1133671A (en) | Method for making metallic glass powder and product | |
US5855642A (en) | System and method for producing fine metallic and ceramic powders | |
CA1330622C (en) | Hydrometallurgical process for producing finely divided iron based powders | |
Shanmugavelayutham et al. | Plasma spheroidization of nickel powders in a plasma reactor | |
US4781741A (en) | Process for producing spherical glass particles | |
JPH06172817A (en) | Production of quenched metal powder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE DE FR GB NL SE |
|
17P | Request for examination filed |
Effective date: 19850130 |
|
17Q | First examination report despatched |
Effective date: 19860930 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB NL SE |
|
REF | Corresponds to: |
Ref document number: 3483189 Country of ref document: DE Date of ref document: 19901018 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19941229 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19950105 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19950125 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19950130 Year of fee payment: 12 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 84900776.0 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19950131 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19950228 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19960106 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19960107 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19960131 |
|
BERE | Be: lapsed |
Owner name: GTE PRODUCTS CORP. Effective date: 19960131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19960801 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19960106 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19960930 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19960801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19961001 |
|
EUG | Se: european patent has lapsed |
Ref document number: 84900776.0 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |