Patent Grant
7422720
1. Field of the Invention
This invention relates in certain embodiments to high density, nontoxic articles such as shots used as projectiles in shotgun shells and the like.
2. Description of the Related Art
Lead has traditionally been used as a material for shot pellets for hunting, especially hunting for birds, because of its high density and low melting point that lend itself to ease of manufacture and highly predictable ballistic characteristics. The majority of these pellets fall to the ground without hitting the target. Some of them settle on the bottom of the wetlands and lakes. Over time the spent lead pellets accumulate to a point that some waterfowl have shown signs of lead poisoning because they ingested lead pellets while in search of food and also the grit to assist in digestion of the food. This has led to the ban of lead shot pellets for waterfowl hunting in the U.S., Canada, and other countries.
Because of market demand, considerable effort has been devoted to searching for a viable lead substitute that can be economically produced and at the same time possesses the predictable ballistic characteristics of the lead shot pellet, such as uniform pattern density with a wide variety of shotgun chokes and barrel lengths, and uniform muzzle velocities with various smokeless powders. There are no comparable metals that possess all of the desired characteristics. Those metals that are somewhat close to lead in density are not satisfactory substitutes as a result of other drawbacks, such as high cost, radioactivity, high melting point, or other properties.
Various approaches have been proposed to formulate a mixture of metals and in some cases using polymers. Additionally, various methods have been attempted to process these mixtures for the final product. Despite these prior efforts, the products made according to these materials and processes have some shortcomings as discussed below.
Steel was selected as the most practical substitute, based on methods of production, cost, ballistics, and its nontoxic nature. However, steel shot pellets have a density of about 7.5 to about 8.0 g/cm3 as compared to lead alloy shot pellets which have a density of about 10 to about 11 g/cm3. Density differences between shots of the same gauge will perform differently in the trajectory and firearm recoil when powered by the same charge. Additionally, steel shot pellets do not deform, and have a definite tendency toward center density regardless of choke. Especially for the large size steel shots, they do not pattern perfectly from tightly choked barrels because such charges do not swage down well to flow smoothly through the choke. The wedging and bridging were believed to be the reasons in an overly choked condition. To compensate for the density difference, hunters have been using two or three larger gauge shot pellets in the shotshell load. Unfortunately, the larger shot pellet size reduces the total number of shot pellets that can be loaded in the predefined shotshell case; this in turn deteriorates the pattern density. Because of the hardness of the steel shot pellet, it is required to have a thicker and harder plastic to protect the bore from the ravages of the steel shot pellets. This requirement further reduces the case volume available for the shot pellets. In order to increase the case volume to accommodate more steel shot pellets, the wad has been redesigned to eliminate the collapsible leg section.
The larger diameter steel shot pellets suffer more disadvantages. The larger steel shot pellet will lose velocity quicker than the smaller high density shots. Also, the steel shot pellet will not penetrate as well because of its larger frontal section. This, coupled with low density, loss of velocity due to drag force, and the inferior pattern density previously mentioned, have resulted in an increased number of crippling shots. Hunters have been known to reduce the range over which he or she will try to take game by as much as 25%. Also, because the steel shot pellets lose momentum over the flight range, they require a lengthened lead. Some manufacturers have employed special powder to drive up the muzzle velocity, but these powders also increase the barrel pressure which causes safety concerns. All of these issues cause a great deal of confusion and frustration to the hunting community.
Nontoxic shot products currently in the market are either too hard or too soft, too frangible or too rigid, or too abrasive. Products that are too hard or too rigid damage the gun barrel and have a strong tendency to ricochet when hitting a hard surface. Products that are too soft tend to leave some rub off particles in the gun barrel and deform too much at firing and in flight, which causes deterioration in the shot pattern and final impact energy and energy transfer. It is also harder for a soft shot to penetrate the animal to make a clean kill. Products that are too frangible tend to crack during set back (firing), and in flight; this will cause drag in flight and cause the shot to lose momentum. It also tends to cause the shot to disintegrate upon impact, thus impeding penetration and causing the energy to not transfer onto the animal.
The majority of the prior nontoxic shots have not proved to be commercially viable primarily due to high equipment cost, high process operating cost, inferior density and hardness characteristics compared to lead and lead alloy.
One embodiment of the present invention is a nontoxic shot for various applications. The shot preferably contains tungsten, and may be a sintered nontoxic shot pellet for ammunition with high accuracy in specific gravity and tight tolerance in size. Preferably, the shot is made using a mechanical agitation or tumbling process, to produce precise control over the size and sphericity of the shot, while also maintaining a high density and relatively low hardness. In one embodiment, the shot has a density of at least 10 g/cm3, and a Vickers hardness HV of about 230 or less.
Another embodiment of the present invention is a composition for a shot that varies throughout the cross section of the shot, and also in a precise manner. In one embodiment, a sintered shot has a predetermined transition of density and transition of hardness reading at different layers/depths of the shot. More preferably, a sintered high density shot is provided containing tungsten and having a predetermined combination of size tolerance, accuracy in each layer's density, and accuracy in aggregate density. In one example having three distinct layers, the surface hardness measured at near the shot's generally spherical surface measures about HV 200 or lower, more preferably about HV 100 or lower, and the core hardness measures about HV 200 or lower, more preferably about HV 110 or lower.
After a shot is formed, a tin coating may optionally be plated or hot dipped on the outer surface of the shot.
In accordance with preferred embodiments of the invention, multiple variations in material can be used to form a spherical shot. For example, a single layer shot may be formed, with or without an additional tin coating. In another example, a dual layer shot may be formed, having a core and an outer layer, with or without an additional tin coating on the outer surface of the outer layer. In another example, a three layer shot may be formed, having a core, an intermediate layer, and a surface layer. This three layer shot may have varying hardness and/or density between the layers, and may or may not have a tin coating on the outer surface of the surface layer.
In one embodiment, an ammunition projectile is provided comprising a first component comprising tungsten, and a second component comprising at least one of copper, iron and nickel. The projectile has a density of at least 10 g/cm3 and a Vickers hardness HV of about 230 or less. In a preferred embodiment, the ammunition projectile comprises primarily tungsten, and is uniformly layered and sintered. The second component may comprise copper, iron and nickel. The projectile may be made by mechanical agitation, and may be spherical, with a ball diameter variation of about 0.0068″ or less. The density of the projectile may be about 10 to 15.5 g/cm3, and may have a diameter suitable for use as a shot in a shotgun shell.
In another embodiment, an ammunition projectile comprises powder components comprising tungsten and at least one of copper, iron and nickel, and a binder. The powder components are bound by the binder, grown in layers and sintered to form a sphere. In one embodiment, the sphere has a substantially uniform ball diameter variation, such as about 0.0068″ or less. The powder components may comprise primarily tungsten, and copper, iron and nickel. The sphere may have a density of about 10 to 16 g/cm3, more preferably about 10 to 13.5 g/cm3. The projectile may be a shot suitable for use in a shotgun shell, and may have a diameter from about 0.05″ to about 0.36″, more preferably from 0.070″ to 0.220″.
In another embodiment, a lot of ammunition projectiles is provided. The lot comprises a plurality of spherical shots, each shot comprising a first component comprising tungsten, and a second component comprising at least one of copper, iron and nickel. The first and second components are bound together with a binder and sintered to form the shots. The shots comprise uniformly grown layers, and the plurality of spherical shots have a lot diameter variation of about 0.01″ or less. In other embodiments, the lot diameter variation may be about 0.008″ or less, about 0.006″ or less, or even about 0.005″ or less. Each spherical shot may have a density of about 10 to 16 g/cm3, more preferably about 10 to 13.5 g/cm3. Each spherical shot may have the same diameter in the range of 0.070″ to 0.220″.
In another embodiment, an ammunition projectile having a desired aggregate density is provided. The projectile comprises a plurality of layers of different compositions, the plurality of layers including a relatively soft surface layer and a relatively hard section within the surface layer. The desired aggregate density is in the range of about 9 to 16 g/cm3. The projectile may be spherical, and the plurality of layers may be concentrically arranged. The relatively hard section within the surface layer may be a core, or may be an intermediate layer, further comprising a relatively soft core. The surface layer may have a density of between about 8 and 10 g/cm3, and the core may have a density of between about 8 and 10 g/cm3. The relatively hard section may have a density of between about 11 and 18 g/cm3. The desired aggregate density may be in the range of about 9.4 and 15 g/cm3. In one embodiment, the relatively hard section has a hardness of between about HV 200 and HV 270 and the surface layer has a hardness of about HV 200 or lower. In one embodiment, the core and surface layer have a hardness of about HV 200 or lower and the intermediate layer has a hardness between about HV 200 and HV 270. The projectile may be substantially lead free, and the surface layer may comprise primarily iron and the relatively hard section may comprise primarily tungsten. The projectile may be spherical and form a shot suitably sized for use in a shotgun shell.
In another embodiment, a method of making an ammunition projectile having a predetermined aggregate density is provided. One or more constituents is selected in powdered form having a density substantially higher than the predetermined aggregate density. One or more constituents is selected in powdered form having a density substantially lower than the predetermined aggregate density. In combination, the constituents having densities substantially higher and substantially lower than the predetermined aggregate density provide an aggregate density substantially equal to the predetermined aggregate density. The powdered constituents are agitated with a binding agent to cause the powdered constituents to form pellets. The pellets are sintered to form projectiles having substantially the predetermined aggregate density.
The powdered constituents having a density substantially higher than the predetermined aggregate density may be selected from the group consisting of virgin tungsten, ferrotungsten, tungsten carbide, tungsten alloys and scrap tungsten. The powdered constituents having a density substantially lower than the predetermined aggregate density may be selected from the group consisting of Fe, Ni, Cu and combinations thereof. The powdered constituents may be agitated using an agitator selected from the group consisting of a drum, disk, dish and pan. Agitating the powdered constituents with a binding agent causes the pellets to agglomerate in generally uniform layers. The predetermined aggregate density may be about 10 to 15.5 g/cm3, and the sintered projectiles may have a diameter in the range of 0.070″ to 0.220″. Sintering the pellets may cause the pellets to shrink about 10% to 25%. The pellets may form projectiles suitable for use as shots in a shotgun shell. In one embodiment, distinct mixes of powdered components may be agitated in stages to form pellets having layers of different compositions.
In another embodiment, a method of making spherical shots comprises providing powders comprising tungsten and at least one of copper, iron and nickel. The powders are added to a mechanical agitator while directing liquid binder into the mechanical agitator. The agitator is rotated while continuing to add the powders, whereby powders wetted by the liquid binder agglomerate to form densified balled materials. The method may further comprise screening the densified balled materials to eliminate materials outside of a desired diameter range. The powders may form densified balled materials having a diameter in the range of about 0.05″ to 0.36″. The powders may comprise copper, iron and nickel. The powders may form densified balled materials having a density of about 10 to 16 g/cm3, more preferably of about 10 to 13.5 g/cm3. The method may further comprise sintering the densified balled materials, such as in a first lower temperature stage and at a second higher temperature stage. The mechanical agitator may comprise a rotating drum. The powders may form densified balled materials at a rate of about 0.1 to 1 mm/hour.
In another embodiment, a method of making ammunition projectiles is provided. A first mix of powdered components is provided, and the first mix is agglomerated with a binding agent to form a pellet core having a first composition. A second mix of powdered components is provided, and the second mix is agglomerated with a binding agent to form a layer surrounding said pellet core having a second composition. The pellet core and the layer are sintered to produce the projectiles.
In one embodiment, the layer surrounding the pellet core may be an intermediate layer, and the method may further comprise providing a third mix of powdered components, and agitating the third mix of powdered components with a binding agent to form a surface layer surrounding the intermediate layer having a third composition. The first composition and third composition may be substantially the same. After sintering, the surface layer and the core may be relatively softer than the intermediate layer. After sintering, the surface layer and the core may have a density between about 8 and 10 g/cm3 and the intermediate layer may have a density between about 11 and 18 g/cm3. In another embodiment, the layer surrounding the pellet core is a surface layer. After sintering the surface layer may have a density between about 8 and 10 g/cm3 and the core may have a density between about 11 and 18 g/cm3. The first mix and the second mix may comprise tungsten and at least one of iron, copper and nickel. The sintered projectiles may form shots suitable for use in a shotgun shell. The pellet core and the layer surrounding the pellet core may have different hardnesses.
In aerodynamics, parasitic drag is the force caused by moving a solid object through a fluid such as air. Parasitic drag is made up of many components, the most prominent being form drag. The general size and shape of the body is the most important factor in form drag; bodies with a larger apparent cross-section will have a higher drag than thinner bodies. “Clean” designs, or designs that are streamlined and smoothed also contribute to achieving minimum form drag. Form drag follows the drag equation:
D=½(Cd)(ρ)A(V2)
Where
D=drag force
Cd=drag coefficient
ρ=density of fluid
A=reference area
V=velocity of the projectile relative to the fluid
Inarguably, smoother objects can have much lower values of Cd; everything being equal, a precise sphere with a smoother surface will give minimal drag force. More importantly, a group of such high quality spheres will travel in a cohesive way toward a target thus give the best density pattern and maximum delivered energy.
Water fowl loads are regarded as high performance use for which the market often demands high quality shots. The manufacturing process disclosed herein provides high quality nontoxic high density shots that not only have predictable ballistic characteristics during launch, but also have superior loading characteristics for smooth charge during fabrication. This benefits both the manufacturer and general public reloader alike.
In a first embodiment of the invention, a high density, nontoxic shot is provided that is generally consistent in material construction and composition throughout the cross section of the shot. The nontoxic shot is substantially lead-free. As used herein, the term “shot” refers to an ammunition projectile that may be in the form of a pellet, sphere, ball or other small projectile used, for example, to form a charge of a shotgun. Although the preferred embodiments are described with respect to shots, it will be appreciated that embodiments of this invention may be applicable to any suitable type of ammunition projectile, such as bullets and buck shots.
The shot according to this first embodiment preferably comprises tungsten as a first component and preferably copper and/or iron as a second component. In one embodiment, the shot comprises tungsten as the primary component, and may also comprise secondary components comprising copper and/or iron. The term “primary” or “primarily” as used herein indicates that there is more of this component than any other component, although it will be appreciated that in some embodiments, there may be less tungsten than another component. Tungsten may be provided in the form of virgin tungsten, ferrotungsten, tungsten carbide, tungsten alloys and even scrap tungsten. In one embodiment, nickel may also be used as a secondary component. In other embodiments, polymers may also be used as secondary components. Alternatively, compositions may be used with a relatively high amount of copper (e.g., about 19% or more), and substantially no nickel, as nickel can be harmful to small creatures that may be food to fish. Tables 1 and 2 illustrate preferred compositions for a tungsten shot without nickel having different aggregate densities. Percentages as provided herein are in weight percent.
Tables 3A, 3B and 3C illustrate alternative compositions for a tungsten shot also containing nickel. These compositions have a relatively low amount of nickel (e.g., about 7% or less), and less copper than in the embodiments above, to minimize any harmful effects of the nickel content.
In certain preferred embodiments, tungsten can be provided in the range of about 30 wt % to about 80 wt %, more preferably about 35 wt % to about 75 wt %, and may be provided in amounts greater than about 40 wt %, about 45% wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, or about 70 wt %, depending on the desired final density of the shot. Copper may be provided in ranges from about 10 wt % to about 30 wt %, more preferably about 10 to 20 wt %, and even more preferably about 11 to 17 wt %, such as when provided in a composition with tungsten, nickel and iron. Nickel may be provided in an amount of about 7 wt % or less. Iron may be provided in an amount of about 10 to 60 wt %, more preferably about 10 to 40 wt %, with higher amounts of iron generally correlating to smaller amounts of tungsten. It will be appreciated that specific combinations of compositions may be selected to optimize not only the density of the material, but also to optimize the hardness of the shot as well as the ability of the materials to agglomerate and form a uniform, layered structure, described further below.
Although the shot examples provided above illustrate a density of between about 10 and 13.5 g/cm3, it will be appreciated that shots in accordance with the preferred embodiments can be made of any desired density, for example, between about 10 and 16 g/cm3, more preferably between about 10 and 15.5 g/cm3, even more preferably between about 10 and 15 g/cm3. In one preferred embodiment, the shot may have a density of less than 13.5 g/cm3, even more preferably about 11 to 12 g/cm3.
Referring in more detail to the drawings,
The mixed powders are then filled into an appropriate processing apparatus (step 120). One preferred form of the apparatus is illustrated in
The agitator 22 can be equipped with air atomized spray nozzles 24 directing binder flow 44 (step 130) to a powder section 46 on the rotating drum 26. As binder flows into the drum,
In one embodiment, the agitator 22 has a size of 22 inches in diameter, and can be operated under the following parameters.
The agitator preferably uses a liquid binder, more preferably only water. In other embodiments, the binder may be an organic or inorganic binders. Examples of suitable organic binders include, but are not limited to CMC (carbo-methyl-cellulose), alcohols, paraffin, polyvinyl alcohol (PVA), starches, and gums. Examples of inorganic binders include, but are not limited to, alkali silicates, alum, gypsum, lime, and water.
The spheres preferably grow in layers due to particle adhesion, whereby forces between spheres are caused by liquid bridges. Capillary pressure and tensile strength of moist particles are associated with each other, and are influenced to a great extent by the amount of liquid that is present in the pore volume of the agglomerate. With increasing liquid saturation, more and more pores are filled and the liquid bridge and the saturated pores models coexist. The adhesion force of a liquid bridge is proportional to the surface tension α, the particle diameter x, and a function of the liquid bridge angle β, the angle of contact δ, and the dimensionless quotient a/x, which represents distance at the coordination point. As shown in
AiL=αxf(β,δ,a/x)
Further details are described in Wolfgang Pietsch, Agglomeration Processes: Phenomena, Technologies, Equipment (Wiley-VCH Verlag GmbH, Weinheim, 2002), page 58, incorporated by reference above.
If desired, the spraying of the binder into the drum may optionally be turned on and off as needed to ensure uniform agglomeration. Optionally, choppers may also be used to avoid unwanted agglomeration or the formation of oversized conglomerates. For example, a high speed chopper, knife head, accelerator, intensifier, turbine, mill or other suitable tool (all referred to herein generically as a “chopper”) is used to destroy undesired agglomerates which hamper mixing. Choppers can be applied at any suitable point in the process, and may operate at high speeds, e.g., in excess of 500 rpm, 1000 rpm or 1800 rpm. Choppers also assist in distributing binder liquid more uniformly.
After the spheres have grown to an appropriate desired size, precise control over the size of the spheres may be maintained by using a screening process in step 140. In one embodiment, screens may be used through which the spheres may be passed. A first screen may be used which has a minimum pore diameter, such that any spheres that pass through the screen will be rejected. These rejected spheres can be recycled into the agitator until further growth makes them of a potentially viable size. A second screen may be used which has a maximum pore diameter, such that only spheres that pass through the screen may be accepted for sintering. Spheres that exceed the pore size of the screen can be crushed and then recycled as powder in the agitator.
With the spheres that have passed the screening process, a visual inspection may be used to ensure whether the shots meet desired specifications (step 150). In one method, a lot of 100 g of shots is taken, and the number of pieces of shots is counted. If the number falls within a desired range, this reflects that the desired average density of the shots has been achieved. In another method, shot diameters can be measured using a micrometer or Vernier calipers along multiple axes of a shot to determine whether the shot has substantially uniform sphericity, as described below. Shots that do not meet specifications can be recycled such as by crushing back into the process.
Spheres that have passed the screening process and a visual inspection, if performed, may proceed to step 160. At step 160, a determination is made whether a multi-layer shot of differing compositions between distinct layers is to be formed. The formation of multi-layer shots is described in further detail below. For shots formed according to the first embodiment, the process continues to step 170.
The spheres are then sintered, for example in a first stage at about 650° C. for about 1.8 to 2 hours, and then at a second stage at about 1380° C. for about 1.8 to 2 hours for a Ni containing mix with Cu, and about 1450° C. for a mix without nickel. Other suitable sintering conditions may also be used. From the unsintered, green shot to the sintered shot, the spheres preferably shrink between about 10% to 25%, more preferably about 15% to 20% in diameter. Table 5 illustrates examples of shrink ratios to form shots of certain size ranges:
The agitation process desirably provides precise control of a final, sintered product by operating the agitator in a continuous, prolonged and controlled manner. Moreover, tight control over the ratio of particles in the sintering mix further contributes to precise control in the final sintered product. No grinding or polishing is needed to achieve tolerance prescribed.
The precision and control over the processing of the shot allows for bulk quantity production in a very wide range of sizes, for example, from 0.070″ to 0.220″ in diameter, selected and processed to have very high tolerance. Shots can be made into any desired diameter suitable for use in a shotgun shell, for example, between about 0.05″ to about 0.36″, and more particularly 0.100″, 0.110″, 0.120″, 0.130″, 0.150″, and 0.180″. Tolerance may be measured by the ball diameter variation of a sphere, e.g., by comparing the largest diameter of a sphere to the smallest diameter of the same sphere, and can be ensured using the screening process described above. A lot diameter variation can also be measured, comparing the largest diameter of any sphere to the smallest diameter of any sphere. In one embodiment, the lot diameter variation is preferably about 0.01″ or less, more preferably about 0.008″ (about 0.20 mm) or less, more preferably about 0.006″ (about 0.15 mm) or less, even more preferably about 0.005″ or less. The ball diameter variation is usually about ½ or larger of the lot diameter variation, more preferably about 50 to 85% of the lot diameter variation (i.e., about 0.004″ to 0.0068″ or less, more preferably about 0.003″ to 0.0051″ or less, even more preferably about 0.0025″ to 0.00425″ or less). Thus, no pressing, compacting or casting is required, making for exceptional efficiency in making smaller shots that are very uniform in size.
Shots formed according to the first embodiment preferably have a desired hardness, for example about Vickers hardness HV 230 or less. Vickers hardness may be measured using a suitable Vickers hardness machine, for example using forces of 1, 2, 5, 10, 30, 50 and 100 kgf. In one particular embodiment, shots formed according to the method described above and tested using 30 kgf provides a Vickers hardness of between about HV 105 and HV 132. An alternative measurement of hardness may use a Rockwell hardness test.
In one embodiment, the shot preferably has a hardness of about 86 HR15T or less.
In a second embodiment of the invention, in the flow chart of
In one embodiment, a high density nontoxic shot is provided that has a generally soft core, a rugged intermediate layer, and a soft surface layer. Each of the layers is preferably spherical in shape and have the same center. The specific weight of each layer is preferably different from the next layer, selected to allow a wide range of aggregate density, no matter the production method used. In another embodiment, a two layer shot may be formed having a rugged core, and a soft surface layer. Shots with other numbers of distinct layers may also be provided.
The composition of each of the layers may be selected to produce the desired density and hardness. Each of the layers having different composition may preferably be formed from substantially lead-free compositions comprising tungsten as a first component, and iron, copper and/or nickel as additional component(s). For example, compositions taken from Tables 1-3C and used for shots made according the first embodiment above may be used for the intermediate layer. For the core and surface layers, less or no tungsten may be used. For example, in one embodiment, about 10% W or less may be used, with greater than about 60% Fe, and between about 4 and 15% Ni and about 10% and 20% Cu. In one preferred embodiment, the surface layer may have about 10% W, about 63% Fe, and about 27% Cu and Ni (e.g., about 16% Cu and about 11% Ni), forming a layer with a density of about 9.3 g/cm3.
Table 6 illustrates one example of the aggregate density of a three-layered sphere.
In other embodiments, the aggregate density of the three-layer shot may correspond to the values provided in Tables 1, 2, 3A, 3B or 3C above.
Tables 7A and 7B illustrate compositions that may be used for the soft inner core and soft surface layer of a three layer shot. For example, the composition in Table 7A may be used for the core and surface layer of a relatively smaller shot e.g., of 0.120″ in diameter, and the composition in Table 7B may be used for the core and surface layer of a relatively larger shot, e.g., of 0.22″ in diameter.
Tables 8A and 8B illustrate compositions that may be used for the harder intermediate layer of a three layer shot. For example, the composition in Table 8A may be used for a relatively smaller shot e.g., of 0.120″ in diameter, and the composition in Table 9B may be used for a relatively larger shot, e.g., of 0.22″ in diameter.
It will be appreciated that the diameter of the core 62, the thickness of the intermediate layer 64, and the thickness of the surface layer 66 may be adjusted to provide the desired balance of density and hardness for the aggregate shot 60. In certain embodiments, the diameter of the core 62 may range from about 1.4 mm to about 2.4 mm, the thickness of the intermediate layer may range from about 0.5 mm to about 1.6 mm, and the thickness of the surface layer may be about 0.2 mm or less. In one embodiment, the surface layer 66 may be about 0.1 mm thick for shots having a diameter from 0.070″ to 0.100″, about 0.15 mm for shots having a diameter from 0.100″ to 0.180″, and about 0.20 mm for shots having a diameter of 0.180″ or greater. For example, for a 0.130″ diameter shot, the core may have a diameter of about 1.6 mm, the intermediate layer may have a thickness of about 0.65 mm, and the surface layer may have a thickness of about 0.2 mm. Generally, taking 0.130″ as an example, the core radius may be about 40 to 60%, more preferably about 50% of the radius of the aggregate shot, the intermediate layer thickness may be about 30 to 50%, more preferably about 40% of the radius of the aggregate shot, and the surface layer thickness may be about 5 to 15%, more preferably about 12% of the radius of the aggregate shot. As with the first embodiment, shots having a diameter in the range of 0.070″ to 0.220″ in diameter, or any diameter suitable for use in a shotgun shell, may be made.
As in the first embodiment described above, a mechanical agitation or tumbling process can be used to achieve high tolerance control over the chemistry and ratio in the powder mix. Continuous, prolonged, and controlled agitation using a drum agitator, for example, also allows the ability to prescribe a transitioned composition so to achieve transition of hardness at different layer of the shot, from core to surface. Multiple powder mixes are provided with selected compositions to add to the agitator in stages to form each desired layer. In one embodiment, drums can be changed in the agitator from the core mix to the intermediate mix, and then drum can be changed back to the core mix to form the surface layer. Thus, in this example, the core and the surface layer have the same composition. Preferably, after each of the core 62, intermediate layer 64, and surface layer 66 are formed, screening such as described above takes place to assure uniformity and sphericity of product. Recycling of metal powder is built into the production process so there is no waste and very little scrap material. The shot can be sintered such as described above.
As with the first embodiment described above, a slow growth process is used to ensure sphericity of the formed spheres. In one embodiment, the core is grown in the agitator over about 2 to 3 hours, the intermediate layer is grown in the agitator for about 3 to 5 hours, and the surface layer is grown in the agitator over about 1 hour. Overall, the growth rate of the spheres may be in the range of about 0.1 to 1 mm/hour, more preferably about 0.1 to 0.5 mm/hour, and even more preferably about 0.1 to 0.3 mm/hour.
In one embodiment, the core 62 has a density of between about 8 and 10 g/cm3, the intermediate layer 64 has a density of between about 11 and 18 g/cm3, more preferably between about 11 and 13.5 g/cm3, and the surface layer 66 has a density of between about 8 and 10 g/cm3. The aggregate density of the shot 60 can be adjusted, depending on the thickness of each layer, to produce densities in the range of about 9 to 16 g/cm3, more preferably between about 9.4 to 15 g/cm3, even more preferably between about 10 and 13 g/cm3, and even more preferably between about 11 and 12 g/cm3.
It will be appreciated that for a two layer shot, the rugged core may have a density between about 11 and 18 g/cm3, and the surface layer may have a density between about 8 and 10 g/cm3. The core of the two layer shot may have compositions such as provided above for the intermediate layer of the three layer shot, and the surface layer of the two layer shot may have compositions such as provided above for the surface layer of the three layer shot. In one embodiment, the core of a two layer shot may have the compositions provided in Table 9A and 9B below. For example, the compositions in Table 9A may be used for the core of a smaller shot, e.g., a 0.07″ diameter shot, and the compositions in Table 9B may be used for the core of a larger shot, e.g., a 0.22″ diameter shot. The compositions in Tables 10A and 10B may be used for the surface layer of the two layer shot; for example, the compositions in Table 10A may be used for a smaller shot, e.g., a 0.07″ diameter shot, and the compositions in Table 10B may be used for a larger shot, e.g., a 0.22″ diameter shot. The core and surface layer of a two-layer shot may have thicknesses such as described above. The aggregate density of the two layer shot may correspond to the values provided in Tables 1, 2, 3A, 3B or 3C above.
In the three layer shot, the core 62 and surface 66 may have a hardness of about HV 200 or lower, more preferably about HV 110 or lower, even more preferably about HV 100 or lower. In one embodiment, the surface hardness is between about HV 105 and HV 151, and the core hardness is between about HV 105 and HV 120. The hardness of the intermediate layer 64 may be between about HV 200 and HV 270, more preferably between about HV 200 and HV 220. In a two layer shot, in one embodiment, the surface layer hardness may preferably be about HV 105 or less, and the core hardness may preferably be between about HV 105 and HV 196.
An alternative measurement of hardness may use a Rockwell hardness test. In one embodiment, the surface layer of a two layer or three layer shot is preferably about 80 HR15T or less, more preferably about 69 HR15T or lower. The relatively hard layer (e.g., the core of a two layer shot or the intermediate layer of a three-layer shot) will have a higher hardness value, but preferably will not be too high, and in one embodiment, will have a value of about 86 HR15T or less.
After the shot is formed into a sphere and sintered, tin, copper or zinc can be plated or hot dipped onto the outer surface of the shot. This layer helps to make the shot softer and protect it from oxidation.
Advantageously, the soft core and soft surface layer of the shot of
The softness or hardness of the layers or compositions as measured herein are indicative of the ability of the shot to deform upon impact. Other suitable measurements made also be used, such as by measuring the relative ductility of the material or layer, such that a more ductile material will plastically deform substantially before fracture. The multiple layer shots as described above are manufactured to provide desired deformation of the shot upon impact with a target. For example, in a two layer or three layer shot, the softer outer layer has relatively higher ductility than the core or intermediate layer, allowing the material to deform and spread outwardly upon impact. This enables a greater transfer of energy to the intended target, with increased surface area upon contact. With the three layer shot in particular, where the inner core and the surface layer are both made of a relatively softer, more ductile material, the shot upon impact will desirably flatten to impart greater energy to the target.
It will be appreciated that the methods described above can be modified to form shots of various compositions. For example, a shot can be made with a relatively soft core and a relatively hard surface. Alternatively, a shot can be made with a relatively hard core, a relatively soft intermediate portion and a relatively hard surface.
Soft and hard powder mixes may be selected having desired compositions to produce layers of desired hardness and/or density. In one embodiment, hard powder mixes comprise a significant amount of tungsten, preferably about 60 wt % or more, about 65 wt % or more, or about 70 wt % or more. These hard powder mixes may have densities greater than about 12 g/cm3, more preferably greater than about 13 g/cm3, even more preferably greater than about 14 g/cm3. Softer powder mixes comprise less tungsten, preferably about 30 wt % or less, more preferably about 20 wt % or less, even more preferably about 10 wt % or less. These softer powder mixes may have densities less than about 10 g/cm3, more preferably less than about 9 g/cm3, even more preferably less than about 8 g/cm3.
Shots produced according the methods described above compare favorably to shots formed by prior art processes such as by compacting.
Comparing
The grains are also generally uniform in size. For example, preferred embodiments will have about 80% or more of the grains with a diameter less than a desired diameter grain size, for example, about 10 microns. In another embodiment, about 90% or more, or even about 95% or more, of the grains will have diameters less than the desired diameter grain size. The desired diameter grain size may have different values, for example, about 15 microns, about 20 microns, about 25 microns, 30 microns, etc., depending on the composition. In another embodiment, general uniformity in grain size can be determined based on whether a certain percentage of the grains, for example, about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more, or about 95% or more of the grains, fall within a certain desired range of grain diameters. This range may be, for example, about 10 microns, about 15 microns, about 20 microns, about 25 microns, about 30 microns, etc. It will be appreciated that the agglomeration process described above allows formation of shots having this desired combination of small, disperse, uniform grain size, which is desirable to form shots that are substantially spherical and have uniform desired properties (e.g., hardness, ductility) to improve performance of the shot.
In another embodiment, tungsten carbide scrap can be processed to form tungsten powder suitable for the methods above. Scrap typically contains contaminants such as Co and/or Ti, and comes in large or different sizes that can be difficult to process or sort.
In one embodiment, the scrap can be processed using an electrolysis method, wherein Co, Ni, Fe and Cu are dissolved in solution to obtain WC and TiC in flake shape. The WC and TiC mixture is taken out and put in a sodium nitrate and/or sodium carbonate solution. The reaction will result in a sodium tungstate NaWO3 solution and non-dissolvable titanium oxide TiO, thus separating W and Ti. Sodium tungstate NaWO3 and dihydrate calcium chloride CaCl are then caused to react, resulting in calcium tungstate CaWO3. Calcium tungstate CaWO3 and hydrochloric acid HCl react to result in tungstate HWO3. The tungstate HWO3 is cleaned and dried, and the dried tungstate HWO3 is heated to high temperature to produce tungsten oxide WO3. The tungsten oxide WO3 is reduced to obtain tungsten powder. Further details on tungsten scrap is described in U.S. Pat. No. 6,447,715, the entirety of which is hereby incorporated by reference.
In another embodiment, tungsten carbide itself may be used instead of tungsten as a raw material. For example, the tungsten powder as described above can be replaced with a tungsten carbide powder, and be used as the core in a two-layer or three-layer shot, the intermediate layer in a three-layer shot, or as the primary component in a single layer, uniformly distributed shot. In an embodiment where tungsten carbide is used in the core of a two-layer shot or the intermediate layer of a three-layer shot, the surface layer may be comprised substantially of only Fe and Cu, without substantially any tungsten.
Tungsten carbide advantageously has a density of about 15.7 g/cm3, which desirably provides a high density product. When formed into a multiple-layer composite shot such as described above, the tungsten carbide can be used as a higher density component, which when combined with a lower density component, can provide a desired aggregate density.
It will be appreciated that compositions with combinations of materials other than those described above may be used. For example, in one embodiment zinc is incorporated into the shot. Nickel, copper and zinc powders may be provided to alloy the layers in solid state sintering. Such an embodiment may include about 15% to 35% Ni, about 40% to 60% Cu, and about 20% to 35% Zn.
Embodiments of the shots described above advantageously provide a shot which is extremely uniform in dimension, density, and surface hardness for cartridge loading and therefore superior in density pattern. The processes described above are dedicated processes, with definitive process input and output criteria, enabling mass production of shots. Therefore, there is no limit on the production size. The shots are advantageously as dense as lead alloy or higher. Shots as produced herein may be provided in multiple layers, making them structurally extremely strong and capable of withstanding impact with maximum penetration power. Shots can be provided with a thick, relatively soft outer layer protect the gun barrel.
It will further be appreciated that articles produced with the compositions and/or methods described above can be used in a variety of other applications. For example, embodiments of the present invention may be applicable to technologies involving radiation shields, x-ray marker, counter weights, ballast weights, golf club weights, golf ball cores, fishing weights, and diving belt weights.
It will be understood that the foregoing is only illustrative of the principles of the invention, and that various modifications, alterations, and combinations can be made by those skilled in the art without departing from the scope and spirit of the invention.
This application claims the benefit of U.S. Provisional Application No. 60/569,793, filed May 10, 2004, the entirety of which is hereby incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1847617 | Lowenstein et al. | Mar 1932 | A |
| 2105528 | Foisy | Jan 1938 | A |
| 2119876 | Corson | Jun 1938 | A |
| 2183359 | Smithells | Dec 1939 | A |
| 2409307 | Patch et al. | Oct 1946 | A |
| 2442155 | Weese | May 1948 | A |
| 2919471 | Hechinger | Jan 1960 | A |
| 2995090 | Daubenspeck | Aug 1961 | A |
| 3123003 | Lang, Jr. et al. | Mar 1964 | A |
| 3363561 | Irons | Jan 1968 | A |
| 3372021 | Forbes et al. | Mar 1968 | A |
| 3623849 | Benjamin | Nov 1971 | A |
| 3785801 | Benjamin | Jan 1974 | A |
| 3888636 | Sczerzenie et al. | Jun 1975 | A |
| 3890145 | Hivert et al. | Jun 1975 | A |
| 3898933 | Castera et al. | Aug 1975 | A |
| 3946673 | Hayes | Mar 1976 | A |
| 3953194 | Hartline, III et al. | Apr 1976 | A |
| 3979234 | Northcutt, Jr. et al. | Sep 1976 | A |
| 4005660 | Pichard | Feb 1977 | A |
| 4027594 | Olin et al. | Jun 1977 | A |
| 4035115 | Hansen | Jul 1977 | A |
| 4035116 | O'Brien et al. | Jul 1977 | A |
| 4138249 | Rosof | Feb 1979 | A |
| 4252577 | Malard | Feb 1981 | A |
| 4274940 | Plancqueel et al. | Jun 1981 | A |
| 4338126 | Vanderpool et al. | Jul 1982 | A |
| 4383853 | Zapffe | May 1983 | A |
| 4428295 | Urs | Jan 1984 | A |
| 4488959 | Agar | Dec 1984 | A |
| 4603637 | Snide et al. | Aug 1986 | A |
| 4621011 | Fleischer et al. | Nov 1986 | A |
| 4643099 | Luther et al. | Feb 1987 | A |
| 4760794 | Allen | Aug 1988 | A |
| 4762559 | Penrice et al. | Aug 1988 | A |
| 4780981 | Hayward et al. | Nov 1988 | A |
| 4784690 | Mullendore | Nov 1988 | A |
| 4850278 | Dinkha et al. | Jul 1989 | A |
| 4881465 | Hooper et al. | Nov 1989 | A |
| 4897117 | Penrice | Jan 1990 | A |
| 4931252 | Brunisholz et al. | Jun 1990 | A |
| 4939996 | Dinkha et al. | Jul 1990 | A |
| 4940404 | Ammon et al. | Jul 1990 | A |
| 4949644 | Brown | Aug 1990 | A |
| 4949645 | Hayward et al. | Aug 1990 | A |
| 4958572 | Martel | Sep 1990 | A |
| 4960563 | Nicolas | Oct 1990 | A |
| 4961383 | Fishman et al. | Oct 1990 | A |
| 4990195 | Spencer et al. | Feb 1991 | A |
| 5000783 | Dingemon et al. | Mar 1991 | A |
| 5069869 | Nicolas et al. | Dec 1991 | A |
| 5072944 | Nakahara et al. | Dec 1991 | A |
| 5088415 | Huffman et al. | Feb 1992 | A |
| H1235 | Canaday | Oct 1993 | H |
| 5264022 | Haygarth et al. | Nov 1993 | A |
| 5279787 | Oltrogge | Jan 1994 | A |
| 5399187 | Mravic et al. | Mar 1995 | A |
| 5464465 | Avotins et al. | Nov 1995 | A |
| 5527376 | Amick et al. | Jun 1996 | A |
| 5713981 | Amick | Feb 1998 | A |
| 5719352 | Griffin | Feb 1998 | A |
| 5740516 | Jiranek, II et al. | Apr 1998 | A |
| 5747724 | Lindgren et al. | May 1998 | A |
| 5760331 | Lowden et al. | Jun 1998 | A |
| 5774780 | Prause | Jun 1998 | A |
| 5786416 | Gardner et al. | Jul 1998 | A |
| 5814759 | Mravic et al. | Sep 1998 | A |
| 5820707 | Amick et al. | Oct 1998 | A |
| 5831188 | Amick et al. | Nov 1998 | A |
| 5847313 | Beal | Dec 1998 | A |
| 5868879 | Amick et al. | Feb 1999 | A |
| 5877437 | Oltrogge | Mar 1999 | A |
| 5905936 | Fenwick et al. | May 1999 | A |
| 5913256 | Lowden et al. | Jun 1999 | A |
| 5917143 | Stone | Jun 1999 | A |
| 5922978 | Carroll | Jul 1999 | A |
| 5950064 | Robinson et al. | Sep 1999 | A |
| 5963776 | Lowden et al. | Oct 1999 | A |
| 6048379 | Bray et al. | Apr 2000 | A |
| 6090178 | Benini | Jul 2000 | A |
| 6112669 | Mravic et al. | Sep 2000 | A |
| 6136105 | Spencer | Oct 2000 | A |
| 6209180 | Amick | Apr 2001 | B1 |
| 6248150 | Amick | Jun 2001 | B1 |
| 6258316 | Buenemann, Jr. et al. | Jul 2001 | B1 |
| 6270549 | Amick | Aug 2001 | B1 |
| 6371029 | Beal | Apr 2002 | B1 |
| 6447715 | Amick | Sep 2002 | B1 |
| 6457417 | Beal | Oct 2002 | B1 |
| 6497746 | Steeghs et al. | Dec 2002 | B1 |
| 6527824 | Amick | Mar 2003 | B2 |
| 6527880 | Amick | Mar 2003 | B2 |
| 6551376 | Beal | Apr 2003 | B1 |
| 6581523 | Beal | Jun 2003 | B2 |
| 6591730 | Beal | Jul 2003 | B2 |
| 6823798 | Amick | Nov 2004 | B2 |
| 20030161751 | Elliott | Aug 2003 | A1 |
| Number | Date | Country |
|---|---|---|
| 2149067 | Jun 1985 | GB |
| WO 9611762 | Apr 1996 | WO |
| WO 9727447 | Jul 1997 | WO |
| WO 0106203 | Jan 2001 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 60569793 | May 2004 | US |
