EP2111317A1 - Poudre de fer alliée par diffusion - Google Patents

Poudre de fer alliée par diffusion

Info

Publication number
EP2111317A1
EP2111317A1 EP08705333A EP08705333A EP2111317A1 EP 2111317 A1 EP2111317 A1 EP 2111317A1 EP 08705333 A EP08705333 A EP 08705333A EP 08705333 A EP08705333 A EP 08705333A EP 2111317 A1 EP2111317 A1 EP 2111317A1
Authority
EP
European Patent Office
Prior art keywords
iron
powder
bullet
anyone
iron powder
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.)
Withdrawn
Application number
EP08705333A
Other languages
German (de)
English (en)
Other versions
EP2111317A4 (fr
Inventor
Johan Arvidsson
Hans SÖDERHJELM
Original Assignee
Hoganas AB
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 Hoganas AB filed Critical Hoganas AB
Publication of EP2111317A1 publication Critical patent/EP2111317A1/fr
Publication of EP2111317A4 publication Critical patent/EP2111317A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/72—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material
    • F42B12/74—Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material of the core or solid body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • 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
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B7/00—Shotgun ammunition
    • F42B7/02—Cartridges, i.e. cases with propellant charge and missile
    • F42B7/10—Ball or slug shotgun cartridges
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
    • 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
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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 metal powder suitable for producing lead free bullets, in particular bullets having a density of approximately 8-15 g/cm 3 .
  • lead Due to a number of factors such as availability, price and material properties lead has been the dominating material for bullet and shot shell manufacturing.
  • the density of lead at room temperature is 11,35 g/cm 3 which is comparably high in relation to many other materials.
  • the high density enables lead-based projectiles to maintain a higher kinetic energy and more accurate flight pattern over long distances than less dense materials.
  • tungsten (W) and bismuth (Bi) are used commercially for production of lead free ammunition with high density.
  • Tungsten has a density of 19,8 g/cm 3 and the toxic effects of tungsten is considered to be comparably limited. Further it would be advantageous if the costs of such bullets can be kept low.
  • the price for tungsten is very dependent on the particle size and purity and very expensive atomised powders are available on the market.
  • tungsten oxide (W03) which is an intermediate product in the production of W, is comparably cheap.
  • US 5,527,376 claims a shot pellet or small arms projectile comprising 40% by weight to 60% by weight tungsten and from 60% by weight to 40% by weight iron prepared by sintering tungsten containing powders having median particle sizes below about 6 microns at a temperature sufficient to form a material consisting primarily of an intermetallic compound of tungsten and iron, a projectile comprising 40-60 wt% W and 60-40 wt% Fe, formed by sintering tungsten containing powder.
  • US 5,950,064 presents a method for the manufacture of lead-free shots with a density equal to or higher than lead.
  • Ferrotungsten typically 70%-80%, by weight, tungsten and the balance iron
  • other iron-tungsten alloys are most preferred due to a relatively low cost when compared to tungsten metals and other tungsten base alloys.
  • US 5,399,187 shows a lead free bullet, comprising: a compacted composite containing a high-density first constituent selected from the group consisting of tungsten, tungsten carbide, ferrotungsten and mixtures thereof; and a lower density second constituent selected from the group consisting of tin, zinc, aluminium, iron, copper, bismuth and mixtures thereof.
  • US 6,112,669 describes a lead- free projectile made from a composition containing about 5-25% by weight tungsten and more than about 97% by weight tungsten plus iron.
  • US 6,527,880 describes a non-toxic shot having a composition of 20-70% W, 10-70% Ni and 0-55% Fe.
  • US 6,640,724 describes a method for manufacturing a frangible projectile from a mixture of powders having a composition that consists essentially of up to 35% ferrotungsten, up to 3% lubricant, and the balance iron.
  • the mixture is compacted at a pressure of between about 138 MPa and about 827 MPa to form a compact.
  • the compact is optionally sintered at a temperature no greater than about 900 0 C.
  • One object of the invention is to provide an iron-based powder and a powder composition which is suitable for manufacturing lead free ammunition.
  • a further objective is to provide a non-toxic projectile manufactured from said iron-based powder.
  • the projectile can be made to have a density in the range of approximately 8
  • g/cm 3 preferably in the range of approximately 10-13 g/cm 3 , more preferably in the range of approximately 10,5-12 g/cm 3 , and even more preferably a density of approximately 11.3-11.8 g/cm 3 ; that the projectile material is non-toxic or at least less toxic than lead to wildlife and the environment; that the projectile can be made magnetic for game-law purposes; that the projectile will less likely fracture or disintegrate upon target impact; - that the projectile will less likely expand or deform upon target impact; that the projectile which, by virtue of ferromagnetic properties, may be readily salvaged for reuse; that the projectile can be manufactured at comparably low costs; that the iron based powder can be produced at comparably low costs; and - that the alloying element(s) in the iron-based powder are evenly dispersed.
  • At least one of the above mentioned objects are solved by providing a diffusion alloyed iron powder having tungsten bonded to the surfaces of the powder particles, which diffusion alloyed iron powder comprises 30-60 wt% tungsten, balance essentially only iron and unavoidable impurities.
  • the diffusion alloyed powder of the invention has been shown to be suitable for producing lead free bullets, in particular when the diffusion alloyed powder is admixed with graphite in an amount of 1-4 wt% C. Therefore a metallurgical powder composition is proposed, which composition comprises: at least 90 percent by weight of the diffusion alloyed iron powder of the invention and about 0.05 to about 2 percent by weight of a lubricant and optionally about 0.05 to about 2 percent by weight of a binder.
  • the composition further comprises 1-4 wt% C in the form of Graphite.
  • a process for producing a diffusion alloyed iron powder which comprises: 30-60 wt% tungsten, balance essentially only iron and unavoidable impurities, said process comprises; a) mixing a tungsten oxide and an atomized iron powder, b) and annealing the mix of step a) under a reducing atmosphere whereby the tungsten oxide is reduced and tungsten is bonded to the surfaces of the iron powder particles of the iron powder.
  • the annealing is performed at a temperature of at least 800 0 C, more preferably at least 900 0 C and at a temperature below 1500 0 C, more preferably below 1200 0 C.
  • the annealing is preferably performed during at least 30 minutes, more preferably at least 45 minutes.
  • the reduced atmosphere comprises essentially hydrogen.
  • a method for producing a bullet comprising: a) providing a powder metallurgical composition including 1) a lubricant, 2) a diffusion alloyed iron powder comprising 30-60 wt% W and at least 40 wt% Fe, and 3) 1-4 wt% C in the form of graphite, b) forming a green body from the powder metallurgical composition; and c) sintering the green body in a reducing or neutral atmosphere, at an atmospheric pressure or below, and at a temperature above 1100 0 C.
  • the green body is formed by cold compaction of the mixture, where preferably the compaction pressure is within the range of 500-1500 MPa, more preferably at least 800 Mpa, and where preferably the temperature during compaction is below 100 0 C.
  • the green body is formed by warm compaction of the mixture, where preferably the compaction pressure is within the range of 500-1500 MPa, preferably at least 800 Mpa, and where preferably the temperature during compaction is within the range of 100-200 0 C.
  • the sintering temperature is in the range of 1100 0 C to 1400 0 C.
  • the sintered density of the bullet produced according to the bullet preferably has a density of at least 10 g/cm 3 , more preferably at least 11 g/cm 3 .
  • Such bullets are suitable as shot gun bullets and hunting bullets.
  • the bullet may be coated with a jacket from the group consisting of tin, zinc, copper, brass and plastic.
  • FIG. 1 is a metallographic picture showing the sintered structure of a W/FE/C -alloy according to the present invention
  • FIG. 2 is a metallographic picture showing the W-particles embedded in the Fe-C matrix of a W/FE/C alloy according to the present invention
  • FIG. 3 is a metallographic picture showing the sintered structure of a bullet manufactured from a diffusion alloyed powder of the invention.
  • DA 1, DA 2 and DA 3 - Three diffusion alloyed iron powders - referred to, in the present application, as DA 1, DA 2 and DA 3 - were prepared. This was done by mixing 227 grams of WO3, from the company H. C. Starck, and 120 grams of different iron powders, iron powder 1, iron powder 2 and iron powder 3 - the numbering of the iron powders corresponding to the numbering of the diffusion alloyed iron powders. I.e. DA 1 was prepared from iron powder 1 and so on. The iron powders are shown in Table 1 and the diffusion alloyed powders are shown in Table 2.
  • Respectively mix of iron powder 1, 2 and 3 and WO3 where heat treated in a continuous furnace during 60 minutes at a temperature of 1000 0 C, the atmosphere being 100% Hydrogen. During this heat treatment, the fine particles of the WO3 powder bonds to the coarser iron powder particles. After cooling the resulting soft cakes were milled, and approximately 300 grams of the diffusion alloyed powders, DA 1, 2 and 3, were obtained respectively. Chemical analysis showed that the resulting diffusion alloyed powders DA 1, 2 and 3 comprised 40 wt% Fe, 60 wt% W and inevitable impurities.
  • compositions were tested. For each composition test samples were produced by filling a form (10mm diameter and 2mm thickness) with the powder metallurgical compositions shown in Table 3. These samples were then compacted at a compaction pressure of 1000 Mpa followed by sintering in a 100% Hydrogen atmosphere during 1 hour and at a temperature of 1325 0 C. For each composition the green density and sintered density was measured as averages from their corresponding test samples. The aim was to create some sort of liquid phase sintering and the additives FeSi, FeB, C and carbonyl nickel were evaluated as seen in Table 3. Table 3
  • composition A As can be seen in Table 3 the best results were achieved for composition A, E and F - all being mixed with 2 wt% C in the form of Graphite (grade UF). The highest sintering density was achieved for composition A, however composition E and F closely followed.
  • FIG. 1 and FIG. 2 show metallographic pictures for composition A.
  • FIG. 1 it can be seen that the porosity is more pronounced in the centre of the specimen and FIG. 2 shows how the W-particles are embedded in the Fe-C matrix.
  • the tungsten content could be further reduced - for a sintered density of 11,8 g/cm3 the theoretical tungsten content is approximately 30 wt%.
  • the sintering temperature may also be reduced, preferably below 125O 0 C while still maintaining liquid phase sintering.
  • a projectile produced from the powder of the invention may have a density in the range of approximately 8-15 g/cm 3 , preferably in the range of approximately 10-13 g/cm 3 , more preferably in the range of approximately 10,5-12 g/cm 3 , and even more preferably a density of approximately 11.3-11.8 g/cm 3 .
  • the projectile of the invention may have a density outside of these illustrative ranges and within further subsets of these ranges.
  • FIG. 3 shows metallographic pictures of a bullet produced from composition A of Table 3.
  • the porosity reduces the tendency for ricochets as well as improves the adherence of the lubricant put on the surface
  • the projectiles are jacketed, compacting could be done in the jacket and sintered therein.
  • the projectiles could be compacted and sintered before being inserted into the jackets. If the projectiles are coated, they would be coated after compacting and sintering.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne une poudre de fer alliée par diffusion caractérisée en ce que du tungstène W est fixé aux surfaces des particules d'une poudre de fer ou à base de fer, la poudre de fer alliée par diffusion comprenant, en % en poids : 30-60 % de W, le reste étant pour l'essentiel seulement du fer et des impuretés inévitables.
EP08705333.6A 2007-01-26 2008-01-21 Poudre de fer alliée par diffusion Withdrawn EP2111317A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US88666407P 2007-01-26 2007-01-26
SE0700193 2007-01-26
PCT/SE2008/050061 WO2008091210A1 (fr) 2007-01-26 2008-01-21 Poudre de fer alliée par diffusion

Publications (2)

Publication Number Publication Date
EP2111317A1 true EP2111317A1 (fr) 2009-10-28
EP2111317A4 EP2111317A4 (fr) 2013-08-07

Family

ID=39644717

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08705333.6A Withdrawn EP2111317A4 (fr) 2007-01-26 2008-01-21 Poudre de fer alliée par diffusion

Country Status (6)

Country Link
US (1) US20100043662A1 (fr)
EP (1) EP2111317A4 (fr)
CN (1) CN101588883B (fr)
BR (1) BRPI0807180A2 (fr)
CA (1) CA2675104A1 (fr)
WO (1) WO2008091210A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012009805A2 (pt) * 2009-10-26 2016-11-22 Minpro Aktiebolag reciclagem de carbetos de tungstênio
TW201430143A (zh) 2012-09-05 2014-08-01 Ferrolegeringar Ab 含有鐵及鎢之丸粒
CN103627941A (zh) * 2013-12-06 2014-03-12 株洲乐泰金属粉末制品有限公司 一种用于猎枪子弹弹芯的钨锡合金球的配方及其制备工艺
RU2606358C2 (ru) * 2015-01-12 2017-01-10 Юрий Генрихович Векслер Способ получения легированных порошков в виброкипящем слое
US10690465B2 (en) 2016-03-18 2020-06-23 Environ-Metal, Inc. Frangible firearm projectiles, methods for forming the same, and firearm cartridges containing the same
US10260850B2 (en) 2016-03-18 2019-04-16 Environ-Metal, Inc. Frangible firearm projectiles, methods for forming the same, and firearm cartridges containing the same
CN112746215A (zh) * 2020-12-25 2021-05-04 北京首钢吉泰安新材料有限公司 一种成分均匀的含低熔点高密度元素钢的冶炼方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
GB598181A (en) * 1945-02-12 1948-02-12 Diffusion Alloys Ltd A process for the coating of metal powders
JPS63297502A (ja) * 1987-05-29 1988-12-05 Kobe Steel Ltd 粉末冶金用高強度合金鋼粉及びその製造方法
JPH0356609A (ja) * 1989-07-21 1991-03-12 Awamura Kinzoku Kogyo Kk モリブデン被覆複合粉末の製造法
US5831188A (en) * 1992-05-05 1998-11-03 Teledyne Industries, Inc. Composite shots and methods of making
US6209180B1 (en) * 1997-03-25 2001-04-03 Teledyne Industries Non-toxic high density shot for shotshells
US20030097907A1 (en) * 2001-11-28 2003-05-29 Carroll Daniel F. Methods of producing composite powders

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DE940712C (de) * 1946-05-22 1956-03-22 Husqvarna Vapenfabriks Ab Auf pulvermetallurgischem Wege hergestellte Legierung mit hoher Kriechgrenze
JPS58481B2 (ja) * 1976-03-12 1983-01-06 川崎製鉄株式会社 低酸素鉄系金属粉末の製造方法および装置
US4954171A (en) * 1987-09-30 1990-09-04 Kawasaki Steel Corp. Composite alloy steel powder and sintered alloy steel
US5264022A (en) * 1992-05-05 1993-11-23 Teledyne Industries, Inc. Composite shot
US5527376A (en) * 1994-10-18 1996-06-18 Teledyne Industries, Inc. Composite shot
JPH0718351A (ja) * 1993-07-07 1995-01-20 Railway Technical Res Inst 焼結集電摺動材料
US5399187A (en) * 1993-09-23 1995-03-21 Olin Corporation Lead-free bullett
US5950064A (en) * 1997-01-17 1999-09-07 Olin Corporation Lead-free shot formed by liquid phase bonding
US6112669A (en) * 1998-06-05 2000-09-05 Olin Corporation Projectiles made from tungsten and iron
US6527880B2 (en) * 1998-09-04 2003-03-04 Darryl D. Amick Ductile medium-and high-density, non-toxic shot and other articles and method for producing the same
FR2784690B1 (fr) * 1998-10-16 2001-10-12 Eurotungstene Poudres Poudres metalliques microniques a base de tungstene et/ou de molybdene et de materiaux de transition 3d
US6640724B1 (en) * 1999-08-04 2003-11-04 Olin Corporation Slug for industrial ballistic tool
US6537489B2 (en) * 2000-11-09 2003-03-25 Höganäs Ab High density products and method for the preparation thereof
WO2003064961A1 (fr) * 2002-01-30 2003-08-07 Amick Darryl D Articles contenant du tungstene et procedes permettant le formage de ces articles
CN100515613C (zh) * 2004-04-22 2009-07-22 杰富意钢铁株式会社 粉末冶金用混合粉体
WO2005102564A1 (fr) * 2004-04-22 2005-11-03 Jfe Steel Corporation Poudre mélangée pour métallurgie des poudres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB598181A (en) * 1945-02-12 1948-02-12 Diffusion Alloys Ltd A process for the coating of metal powders
JPS63297502A (ja) * 1987-05-29 1988-12-05 Kobe Steel Ltd 粉末冶金用高強度合金鋼粉及びその製造方法
JPH0356609A (ja) * 1989-07-21 1991-03-12 Awamura Kinzoku Kogyo Kk モリブデン被覆複合粉末の製造法
US5831188A (en) * 1992-05-05 1998-11-03 Teledyne Industries, Inc. Composite shots and methods of making
US6209180B1 (en) * 1997-03-25 2001-04-03 Teledyne Industries Non-toxic high density shot for shotshells
US20030097907A1 (en) * 2001-11-28 2003-05-29 Carroll Daniel F. Methods of producing composite powders

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2008091210A1 *

Also Published As

Publication number Publication date
US20100043662A1 (en) 2010-02-25
BRPI0807180A2 (pt) 2014-05-27
CA2675104A1 (fr) 2008-07-31
CN101588883A (zh) 2009-11-25
EP2111317A4 (fr) 2013-08-07
CN101588883B (zh) 2012-05-30
WO2008091210A1 (fr) 2008-07-31

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