WO2002046689A1 - Lead free powdered metal projectiles - Google Patents
Lead free powdered metal projectiles Download PDFInfo
- Publication number
- WO2002046689A1 WO2002046689A1 PCT/US2001/031343 US0131343W WO0246689A1 WO 2002046689 A1 WO2002046689 A1 WO 2002046689A1 US 0131343 W US0131343 W US 0131343W WO 0246689 A1 WO0246689 A1 WO 0246689A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- projectile
- lead free
- lead
- ductility metal
- powder
- Prior art date
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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B8/00—Practice or training ammunition
- F42B8/12—Projectiles or missiles
- F42B8/14—Projectiles or missiles disintegrating in flight or upon impact
- F42B8/16—Projectiles or missiles disintegrating in flight or upon impact containing an inert filler in powder or granular form
Definitions
- This invention relates to lead free projectiles. Specifically, this invention relates to lead free projectiles that are significantly less dense than previous lead containing projectiles. More specifically, this invention relates to lead free projectiles that are significantly less dense than previous lead free projectiles, which were designed to approximate the theoretical density of lead.
- the present invention provides lead free projectiles that are not limited by the theoretical density of lead, and thus offers more flexibility in terms of materials used and methods of manufacture.
- the projectiles of the present invention satisfy the need for lead free projectiles without the expense of high cost materials and processing.
- the projectiles of the present invention produce a similar "feel" and mimic the ballistic properties of lead projectiles of similar caliber and size, as well as similar lead free projectiles.
- the present invention provides an alternative to lead that is less dense than lead but still retains similar external ballistic properties.
- the projectiles of the present invention exhibit external ballistic properties similar to previous lead containing and lead free projectiles, especially when fired within ranges of about 100 yards or less.
- the present invention provides a lead free projectile comprising a compacted admixture of a high ductility metal powder and a low ductility metal powder, wherein the low ductility metal powder is less dense than lead and the projectile is less dense than lead.
- the present invention provides a lead free projectile having a density less than the theoretical density of lead.
- the present invention also provides a lead free projectile comprising a compacted admixture of iron powder and at least one powder selected from tin, zinc and alloys and mixtures thereof.
- projectile includes bullet, shot, and other projectiles associated with firearms.
- Projectile as used herein include core, which is formed from the compacted metal powders, as well as the jacketed or unjacketed core that can be loaded into a cartridge to form a round of ammunition. Variations and modifications of both the projectiles and the processes can be substituted without departing from the principles of the invention, as will be evident to those skilled in the art.
- the projectiles of the present invention comprise a mixture of metal powders, and can comprise lubricants and other materials that aid in the manufacture of such projectiles.
- the metal powder is a mixture of at least one high ductility metal powder and at least one low ductility metal powder.
- the high ductility metal powder facilitates cold forming and ease of manufacture of the powder metal mixture into a finished projectile shape by conventional projectile forming technology.
- the low ductility metal powder reduces the overall cost of the powder metal mixture by acting as a filler that does not sacrifice the material properties of the low ductility metal.
- the high ductility metal powder can be a single metal or a mixture of metal powders having high ductility.
- High ductility as used herein means that the stress-strain characteristic of the material will have an almost indistinguishable transition between elastic and inelastic response regions.
- Examples of high ductility metal powders that can be used according to the present invention include tin, zinc, copper, aluminum, brass, and to a lesser extent gold and platinum. To the extent that any material used is more dense than lead, the low ductility metal should be less dense than lead. Of the above high ductility metals that can be used, tin and zinc are.particularly preferred.
- high ductility metal powder or mixture of powders will depend on a variety of factors, including the particular low ductility metal material used, and the ratio of low ductility to high ductility metal powder used in fabricating the projectile.
- the high ductility metal powder comprises a mixture of metal powders
- metals with lower ductility may be used in combination with the preferred high ductility metals to form a compact having high ductility.
- the density of the high ductility metal powder is preferably less than the theoretical density of lead, however, the density of the high ductility metal powder can be greater than lead if the density of the projectile is less than lead.
- the high ductility metal powder consists of a mixture of powders, the mixture can contain metals of varying density. Again, it is preferred that the density of such mixtures be less than the theoretical density of lead, but the density of the mixture can be greater than lead so long as the composite density of the projectile is less than the theoretical density of lead.
- the low ductility metal powder can be a.single metal or a mixture of metal powders having low ductility.
- Low ductility as used herein means that the material will have a well defined transition between elastic and inelastic response regions in the stress- strain characteristic relationship of the material.
- Examples of low ductility metal powders that can be used according to the present invention include iron, steel, stainless steel and nickel. Of these, iron is particularly preferred.
- the selection of a particular low ductility metal powder or mixture of powders will depend on a variety of factors, including the particular high ductility metal material used, and the ratio of low ductility to high ductility metal powder used in fabricating the projectile.
- the low ductility metal powder comprises a mixture of metal powders
- metals with higher ductility can be used in combination with the preferred low ductility metals to form a mixture having low ductility.
- the density of the low ductility metal powder is preferably less than the theoretical density of lead, however, the density of the low ductility metal powder can be greater than lead if the composite density of the projectile is less than lead.
- the low ductility metal powder consists of a mixture of powders, the mixture can contain metals of varying density. Again, it is preferred that the density of such mixtures be less than the theoretical density of lead, but the density of the mixture can be greater than lead so long as the density of the projectile is less than lead.
- the density of the projectile formed from the powders is preferably less than the theoretical density of lead.
- the projectile i comprise about two parts by volume of high ductility metal powder to one part low ductility metal powder.
- the preferred ratio ensures that the compacted metal powder mixture will take on properties, including properties such as ductility and formability that aid in the production of projectiles of the present invention, of the powder metal more . highly represented in the mixture.
- the preferred material properties are those of the higher ductility metal powder, and thus it is preferred that the higher ductility metal powder comprise a higher percentage of the mixture.
- the projectiles of the present invention can be manufactured by a wide variety of methods.
- the projectiles are made by compacting the mixture of metal powders, and then finishing the projectile, if necessary, by sintering, swaging, or otherwise modifying the compacted mixture.
- Other finishing steps can include jacketing the compacted mixture.
- Jacketing can be accomplished by a wide variety of known methods.
- Compacting can be carried out at substantially ambient conditions, without applied heat, or under heated conditions. The method of manufacture will vary depending on a wide variety of parameters, including the desired projectile, the specific composition of the metal powders, the particle size of the metal powders, and other factors that will be obvious to one skilled in the art.
- the low ductility powder When compacting a mixture of metal powders, it is preferred that the low ductility powder have a pre-compaction particle size distribution of about from 44 to 250 ⁇ m. More specifically, a preferred low ductility mixture can have a particle distribution of about 15 to 25% by weight of particles up to about 44 ⁇ m, about from 5 to 70% by weight of particles having a particle size of about from 44 to 149 ⁇ m, and about from 5 to 15% by weight of particles having a particle size of about from 149 to 250 ⁇ m.
- a pre-compaction particle size distribution of about 22% by weight of particles up to about 44 ⁇ m, about 68% by weight of particles having a particle size of about from 44 to 149 ⁇ m, and about 10% by weight of particles having a particle size of about from 149 to 250 ⁇ m.
- the desired particle size distribution can be determined and obtained through a variety of conventional methods, including optical measurements and sifting.
- the particles are also available commercially in specific particle size distributions.
- a preferred high ductility material comprises powder having a pre-compaction particle size distribution of about from 45 to 180 ⁇ m.
- a preferred high ductility mixture can have a particle distribution of about 10-14% by weight of particles up to about 45 ⁇ m, about from 30-50% by weight of particles having a particle size of about 75 ⁇ m, about from 20-30% by weight of particles having a particle size of about 106 ⁇ m, about from 5- 10% by weight of particles having a particle size of about 150 ⁇ m, and about from 2-4% by weight of particles having a particle size of about 180 ⁇ m.
- a pre-compaction particle size distribution for the low ductility metal of about 14% by weight of particles of about 45 ⁇ m, about 48% by weight of particles having a particle size of about 75 ⁇ m, about 28% by weight of particles having a particle size of about 105 ⁇ m, about 7% by weight of particles having a particle size of about 150 ⁇ m, and about 3% by weight of particles having a particle size of about 180 ⁇ m.
- Some embodiments of the projectile of the present invention may be frangible.
- Frangible as used herein, consistent with its use in the firearms and ammunition industry, means that the projectile breaks apart completely upon striking a hard target.
- Frangible lead free projectiles of the present invention can be prepared by a process of manufacture involving only the cold compacting of the high and low ductility metal powders.
- Non frangible projectiles can be made by cold compacting the metal powders, and can also be made by heat treating the cold compacted metal powders to strengthen the bond between the powders.
- Frangibility depends, at least in part, on the particle size distribution of the high and low ductility metals used.
- pre-compaction particle size distribution of about from 15 to 25% by weight of particles up to about 44 ⁇ m, about from 5 to 70% by weight of particles having a particle size of about from 44 to 149 ⁇ m, and about from 5 to 15% by weight of particles having a particle size of about from 149 to 250 ⁇ m. Even more advantageous is a pre-compaction particle size distribution of about 22% by weight of particles up to about 44 ⁇ m, about
- the desired particle size distribution can be obtained through a variety of conventional • methods, including optical measurements and sifting.
- the particles are also available commercially in specific particle size distributions.
- the particle size of each of the powders can vary, depending on a variety of factors such as the ratio of metal powders, and the ratio of the particle sizes of the metal powders.
- the particles be of irregular shape to promote bonding and strength. It has been found that irregularly shaped particles, when used according to the present invention and when used as components in projectiles of the present invention, improve the bonding of the metal powders and contribute to the green strength of the compacted projectiles, as compared to spherical or regularly shaped particles.
- the particle size distributions described above have been found to provide the advantage of integrity of the projectile before and during firing and frangibility upon impact with a target media. While the relationship between particle size distribution and frangibility are not fully understood, it is believed to be a function of the mechanical interlocking of the particles after the cold compaction of the high and low ductility metal powders.
- the preferred particle size distribution has been.found to provide strength to the compacted composite projectiles of the present invention, and is thought to be one factor enabling the formation of unsintered projectiles of the present invention. By providing such increased robustness and strength, the preferred particle size distribution may provide one factor allowing simplified fabrication of the projectiles of the present invention, involving merely the cold compacting of the metal powders.
- the projectiles of the present invention can be manufactured by a process wherein the high and low ductility metal powders of the desired particle sizes are admixed to provide a mixture with the desired ratio of metal powders and if desired, with a desired particle size distribution.
- the high and low ductility metal powders can also preferably be mixed with one or more lubricants or a mixture of lubricants.
- a lubricant aids in removing the projectiles from the mold after compaction is complete. If a lubricant is to be added, it can be added to either metal powder or the mixture of metal powders.
- a preferred lubricant is zinc stearate, which can be used alone or in combination with other lubricants. Up to about 1.0% by weight of zinc stearate can be beneficially added to the mixture of high and low ductility metal powders prior to compaction.. About 0.5% has been found to be particularly satisfactory.
- the admixture is then placed in a die which is designed to provide the desired shape of the projectile.
- a wide variety of projectiles can be made according to the present invention, including shot and bullets.
- the invention is particularly beneficial in bullet manufacture, and especially those having a generally elongated configuration in which a leading end has a smaller circumference than a trailing end.
- the mixture of high and low ductility metal powders is cold compacted at a pressure of about from 50,000 to 120,000 psi, with a pressure of about 100,000 psi being particularly preferred.
- Compacting at a pressure of about 100,000 psi provides the optimal combination of projectile integrity before and during firing and frangibility upon impact with a target.
- the compaction step can be performed on any mechanical press capable of providing at least about 50,000 psi pressure for a dwell time which can be infinitesimally small.
- Presently available machinery operates with dwell times of about from 0.05 to 1.5 seconds.
- a conventional rotary dial press is used.
- a compaction ratio of about 1.8 to 2.3 is preferred.
- Compaction ratio is used herein in the common sense, meaning that the initial volume of power is compared to the volume of the compacted composite that can form a projectile of the present invention.
- the process may be varied in terms of compaction time or pressure, or the process could further comprise heat treatment such as sintering.
- a jacket can be formed around the projectile if so desired.
- Some embodiments of the projectiles of the present invention do not require jackets. The need to incorporate a jacket into the projectiles of the present invention will depend upon the specific mixture and composition of the metal powders used to fabricate the projectile. In other embodiments, a jacket may be preferred for a variety of reasons.
- the jacket can isolate the powdered iron material of the projectile from a gun barrel, preventing erosion of the rifling of the gun barrel which might result from direct contact between the interior surface of the barrel and the powdered iron of the projectile.
- the jacket also helps provide additional integrity of the projectile before and during firing as well as improving the ballistics of the projectile upon firing.
- the jacket material can be selected from those customarily used in the art, for example, metal or polymeric material. Metals which can be used include aluminum, copper, zinc and combinations thereof, with copper or brass being a preferred choice.
- Polymeric materials which can be used include polyethylene and polycarbonate, with a low density polyethylene material being preferred.
- the jacket can be applied by any number of conventional processes, including acid or cyanide electroplating, mechanical swaging, spray coating, and chemical adhesives.
- the preferred method is electroplating.
- a variety of electroplating techniques can be used in the instant invention, as will be evident to those in the plating art.
- the projectiles are cleaned and sealed before the final plating.
- the sealing can be with impregnating methacrylate and polyester solutions.
- a vacuum impregnation is performed immediately after compaction and prior to electroplating.
- This impregnation involves infusion of the formed projectile cores in methacrylate material in a large batch type operation.
- the impregnation step reduces the porosity of the projectiles by filling voids at or near the surface of the projectiles. These voids can contain impurities which might cause corrosion and plate fouling.
- the impregnation step also provides a barrier to prevent collection of plate bath chemicals in the recesses. Such collected chemicals could leach through the plating, discoloring and changing the dimensions of the bullet.
- the projectiles After sealing the surface of the projectiles, they can be plated with jacketing material to deposit the desired thickness of plating metal on the projectiles.
- Acid copper plating is preferably used, which is faster and more environmentally friendly than alternative techniques, such as cyanide copper plating.
- the projectiles After jacketing, the projectiles can be sized using customary techniques and fabricated into cartridges.
- the additional mass of the jacket aids in the functionality and reliability of the projectiles when used with semi-automatic and fully automatic firearms.
- the projectiles of the present invention can have a variety of configurations, including shot and bullets, but are preferably formed into bullets for use with firearms.
- the bullets can have noses of various profiles, including round nose, soft nose, or hollow point.
- Either the bullet or the jacket, if so provided, can include a driving band which increases the accuracy of individual bullets and reduces the dispersion of multiple bullets.
- the invention is further illustrated by the following specific examples, in which parts and percentages are by weight or volume, as indicated in the Tables.
- the examples show various projectiles of the present invention, fabricated according to the process described herein.
- the frangible projectiles can be made non frangible by heat treatment, for example, sintering.
- representative projectiles for each of the group of examples were fabricated into 9mm and .223 caliber bullets, fired and evaluated.
- frangible bullets are prepared from blends of high ductility metal powders, namely tin (Sn), and low ductility metal powders, namely iron (Fe), in the weight percentages indicated in Table I.
- the theoretical density of each blend is determined, and is also reported in Table I. In each Example, the blend has a theoretical density of less than lead.
- the high ductility metal powder has a particle size distribution of about 14% by weight of particles of about 45 ⁇ m, about 48% by weight of particles having a particle size of about 75 ⁇ m, about 28% by weight of particles having a particle size of about 105 ⁇ m, about 7% by weight of particles having a particle size of about
- the low ductility metal powder has a particle size distribution of about 22% by weight of particles up to about 44 ⁇ m, about 68% by weight of particles having a particle size of about from 44 to 149 ⁇ m, and about 10% by weight of particles having a particle size of about from 149 to 250 ⁇ m.
- the powders are intimately blended with 0.15 weight percent zinc stearate using apparatus conventionally used for the handling of metal powders.
- the blends are cold compacted at a pressure of 90,000 psi for 0.15 second on a rotary dial press.
- the bullets are jacketed with copper by electroplating. The bullets are then loaded into cartridges, tested and evaluated, and provide excellent performance characteristics.
- EXAMPLES 11-63 In Examples 11-63, the general procedure of Examples 1-10 is repeated, using blends of zinc (Zn) and iron. The specific blends and their theoretical densities are reported in Tables II and III. The resulting bullets are loaded into cartridges and evaluated, and found to provide excellent performance characteristics.
- EXAMPLES 64-107 In Examples 64-107, the general procedure of Example 1-10 is repeated, using blends of tin and iron. The specific blends and their theoretical densities are reported in Table IV. The resulting bullets are loaded into cartridges and evaluated, and found to provide excellent performance characteristics.
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Battery Electrode And Active Subsutance (AREA)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60132477T DE60132477T2 (de) | 2000-10-06 | 2001-10-09 | Bleifreie metallpulverprojektile |
MXPA03003030A MXPA03003030A (es) | 2000-10-06 | 2001-10-09 | Proyectores de metal pulverizado sin plomo. |
CA002425118A CA2425118C (en) | 2000-10-06 | 2001-10-09 | Lead free powdered metal projectiles |
EP01981408A EP1330626B1 (en) | 2000-10-06 | 2001-10-09 | Lead free powdered metal projectiles |
DK01981408T DK1330626T3 (da) | 2000-10-06 | 2001-10-09 | Blyfrie metalpulverprojektiler |
AU2002213051A AU2002213051A1 (en) | 2000-10-06 | 2001-10-09 | Lead free powdered metal projectiles |
IL15519001A IL155190A0 (en) | 2000-10-06 | 2001-10-09 | Lead free powdered metal projectiles |
KR10-2003-7004926A KR20030048426A (ko) | 2000-10-06 | 2001-10-09 | 무연 분말 금속 발사체 |
BR0114473-1A BR0114473A (pt) | 2000-10-06 | 2001-10-09 | Projéteis de metal em pó isentos de chumbo |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/684,230 US6892647B1 (en) | 1997-08-08 | 2000-10-06 | Lead free powdered metal projectiles |
US09/684,230 | 2000-10-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002046689A1 true WO2002046689A1 (en) | 2002-06-13 |
Family
ID=24747216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/031343 WO2002046689A1 (en) | 2000-10-06 | 2001-10-09 | Lead free powdered metal projectiles |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1330626B1 (zh) |
KR (1) | KR20030048426A (zh) |
CN (1) | CN1479856A (zh) |
AT (1) | ATE384240T1 (zh) |
AU (1) | AU2002213051A1 (zh) |
BR (1) | BR0114473A (zh) |
CA (1) | CA2425118C (zh) |
DE (1) | DE60132477T2 (zh) |
DK (1) | DK1330626T3 (zh) |
IL (1) | IL155190A0 (zh) |
MX (1) | MXPA03003030A (zh) |
WO (1) | WO2002046689A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3429786A4 (en) * | 2016-03-18 | 2019-06-19 | Environ-Metal Inc. | FRIENDLY PROJECTILES FOR FIREARMS, METHODS OF FORMING THE SAME, AND FIREARMS CARTRIDGES CONTAINING SAME |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5760331A (en) | 1994-07-06 | 1998-06-02 | Lockheed Martin Energy Research Corp. | Non-lead, environmentally safe projectiles and method of making same |
US5847313A (en) * | 1997-01-30 | 1998-12-08 | Cove Corporation | Projectile for ammunition cartridge |
US5917143A (en) * | 1997-08-08 | 1999-06-29 | Remington Arms Company, Inc. | Frangible powdered iron projectiles |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH6474A (de) * | 1893-02-27 | 1893-08-15 | Von Foerster Max | Neues Geschoß |
US6536352B1 (en) * | 1996-07-11 | 2003-03-25 | Delta Frangible Ammunition, Llc | Lead-free frangible bullets and process for making same |
US6074454A (en) * | 1996-07-11 | 2000-06-13 | Delta Frangible Ammunition, Llc | Lead-free frangible bullets and process for making same |
US6090178A (en) * | 1998-04-22 | 2000-07-18 | Sinterfire, Inc. | Frangible metal bullets, ammunition and method of making such articles |
-
2001
- 2001-10-09 BR BR0114473-1A patent/BR0114473A/pt not_active IP Right Cessation
- 2001-10-09 AU AU2002213051A patent/AU2002213051A1/en not_active Abandoned
- 2001-10-09 DE DE60132477T patent/DE60132477T2/de not_active Expired - Lifetime
- 2001-10-09 DK DK01981408T patent/DK1330626T3/da active
- 2001-10-09 AT AT01981408T patent/ATE384240T1/de not_active IP Right Cessation
- 2001-10-09 IL IL15519001A patent/IL155190A0/xx unknown
- 2001-10-09 CN CNA018200559A patent/CN1479856A/zh active Pending
- 2001-10-09 CA CA002425118A patent/CA2425118C/en not_active Expired - Fee Related
- 2001-10-09 KR KR10-2003-7004926A patent/KR20030048426A/ko not_active Application Discontinuation
- 2001-10-09 EP EP01981408A patent/EP1330626B1/en not_active Expired - Lifetime
- 2001-10-09 MX MXPA03003030A patent/MXPA03003030A/es unknown
- 2001-10-09 WO PCT/US2001/031343 patent/WO2002046689A1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5760331A (en) | 1994-07-06 | 1998-06-02 | Lockheed Martin Energy Research Corp. | Non-lead, environmentally safe projectiles and method of making same |
US5847313A (en) * | 1997-01-30 | 1998-12-08 | Cove Corporation | Projectile for ammunition cartridge |
US5917143A (en) * | 1997-08-08 | 1999-06-29 | Remington Arms Company, Inc. | Frangible powdered iron projectiles |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3429786A4 (en) * | 2016-03-18 | 2019-06-19 | Environ-Metal Inc. | FRIENDLY PROJECTILES FOR FIREARMS, METHODS OF FORMING THE SAME, AND FIREARMS CARTRIDGES CONTAINING SAME |
EP3429786B1 (en) * | 2016-03-18 | 2023-02-01 | Federal Cartridge Company | Frangible firearm projectiles, methods for forming the same, and firearm cartridges containing the same |
Also Published As
Publication number | Publication date |
---|---|
DE60132477D1 (de) | 2008-03-06 |
CA2425118C (en) | 2009-12-22 |
EP1330626A4 (en) | 2004-10-13 |
AU2002213051A1 (en) | 2002-06-18 |
DK1330626T3 (da) | 2008-05-26 |
BR0114473A (pt) | 2004-01-13 |
MXPA03003030A (es) | 2003-06-24 |
DE60132477T2 (de) | 2009-01-15 |
EP1330626B1 (en) | 2008-01-16 |
CN1479856A (zh) | 2004-03-03 |
CA2425118A1 (en) | 2002-06-13 |
IL155190A0 (en) | 2003-11-23 |
KR20030048426A (ko) | 2003-06-19 |
EP1330626A1 (en) | 2003-07-30 |
ATE384240T1 (de) | 2008-02-15 |
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