Abstract:
Environmentally improved alternatives to lead shot are provided that overcoat a lead coat with a chemically inert polymer bonded thereto by heating lead shot coated with the polymer above the melting point of the lead shot, or by substituting for lead a combination of dense metal and light metal, and either a core/coating bimetallic sphere relationship or a matrix of light metal provided with powder of a heavy metal embedded therein. The composite shot exhibits a density similar to that of lead.

Description:
This is a division of application Ser. No. 07/606,814, filed on Oct. 13, 1990, now U.S. Pat. No. 5,088,415. 
    
    
     FIELD OF THE INVENTION 
     This invention is directed to substitute for conventional lead shot that will substantially reduce or eliminate the release of lead or similar toxins to the environment, or to animals ingesting the spent shot. The invention also pertains to a process for preparing that shot. 
     BACKGROUND OF THE INVENTION 
     It has long been known that lead shot expended, generally in hunting, that remains in the environment poses a significant toxic problem. The most severe problem presented by the spent lead shot is the ingestion by game fowl, particularly water fowl, of the spent shot for grit. Conventional shot, consisting or consisting essentially of lead, can lead to lead poisoning of the bird ingesting the shot. Estimates of water fowl mortality due to this type of lead poisoning ranges as high as 2-3% of all deaths per year. 
     These findings have generated a continual search for alternatives to conventional lead shot. Ultimately, steel (soft ron) shot was proposed as a substitute, as it is less expensive than more inert and softer metals (such as gold), resists erosion and produces no toxic effects when exposed to the acid environment of water fowl stomachs. Unfortunately, the cost of steel shot is higher than the cost of lead shot, and the steel is significantly harder than lead shot. As a result, steel shot can damage the barrels of most commercially available shotguns not designed specifically for shooting steel shot. Moreover, being substantially less dense than lead, steel shot is significantly inferior to lead, ballistically. This results in a high increase in the unnecessary loss of wild fowl due to crippling rather than kill shots. This increase has been estimated to be a higher increase in mortality than that due to lead poisoning. 
     Additionally, lead shot remaining in the environment is a source of lead introduced to the environment, that can be inadvertently included in a variety of food chains, not only water fowl. The natural acidity of rain fall, coupled with many acid environments, leads to leaching of the lead, and potential poisoning of important habitats and environments. 
     One alternative to conventional lead shot is discussed in U.S. Pat. No. 3,363,561, Irons. As described therein, TEFLON is coated over lead shot, for the purposes of preventing lead poisoning. The process as described for coating the lead shot at column 3, lines 19-45 of the Irons patent, uniformly call for the application of TEFLON at temperatures only up to 400° F. so as to avoid deformation of the shot which starts to lose its shape around 425° F. Polymers exhibiting the levels of corrosion resistance and abrasion resistance necessary to be effective in significantly reducing or eliminating lead leaching require temperatures in excess of 400° F. to cure and bond satisfactorily. Most of the processes call for temperatures about 400° F. This results in a thin coating of polymer about an internal lead shot, but no significant bonding between the polymer and the shot. As a result, the polymer is easily peeled from the shot, and in fact, significant erosion or destruction of the polymer coating can occur in the mechanical environment of the shotgun barrel. Accordingly, this alternative has not received success in the industry. 
     It therefore remains a goal of those of skill in the art to provide ballistically acceptable, environmentally safe and lead erosion-free shot. 
     SUMMARY OF THE INVENTION 
     This invention provides shot which yields no, or remarkably low, leaching of lead shot, according to established standards. These and other objects of the invention are achieved in a variety of embodiments. 
     As one preferred alternative embodiment, conventional lead shot is coated with a substantially inert, chemical and abrasion-resistant polymer, such as TEFLON, or its fluorinated polymer variants. The TEFLON is baked in an environment which supports the shape of the lead shot, at a temperature above the melting point of the lead shot. This allows the polymer to be heated to the temperature required to optimally cure and bond the polymer without deformation occurring to the lead shot. Additionally, as the molten shot with the baked polymer coating is allowed to cool, there is an opportunity for mechanical bonding at the lead-polymer interface. As the molten shot with the baked polymer coating is allowed to cool, chemical as well as mechanical bonding occurs at the interface of the lead shot and the coating. As a result, the coating is substantially more adherent to the shot than prior art attempts, giving a dramatic reduction in lead leached from the shot under standard testing methodology. 
     In a second alternative, metals with a specific gravity greater than lead, particularly tungsten or depleted uranium (Udep) are provided with an outer coating of an alternative metal or metal alloy, such as zinc, bismuth, aluminum, tin, copper, iron, nickel or alloys, which when coated about the denser core, will result in an average density comparable to that of lead, e.g., 11.35. This process will also allow average densities of between 9.0 and 17.5 to be obtained which may be desirable for special applications. 
     In a third alternative, a molten preparation of a lighter metal, such as those mentioned above with respect to the bimetallic sphere embodiment, is provided with a powder of denser metals, such as tungsten or depleted uranium. As the melting point of tungsten is substantially above the melting points for all the metals and metal alloys mentioned, and the melting point for depleted uranium is above the majority of the metals and metal alloys mentioned, the resulting suspension can be formed into concentric spheres by conventional methods. 
     In these two latter embodiments, as the shot contains no lead, it cannot release any lead to the environment or animal ingesting the shot. Moreover, the majority of the alternative metals or metal alloys will yield a coating or matrix alloy that is sufficiently soft to be useful in conjunction with existing shotgun barrels. The density can be matched to that of lead, by proper adjustment of the concentration of the heavier and lighter metals. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The shot that is the subject of this invention can be prepared in any dimension, and is desirably prepared in dimensions identical to that of current commercially offered lead or iron shot. Conventional shot is generally prepared by dropping molten lead or other metal preparation through a &#34;shot tower&#34;. In this process, a preparation of molten metal is directed to a sieve positioned at a substantial height over a cooling bath, such as water or oil. As the molten metal, e.g., lead, falls through the shot tower, leaving the sieve, it naturally forms a sphere, and gradually cools in its passage down the tower, which may be as much as 120 feet or more. Finally, it is quenched in the cooling bath, which maintains the spherical shape of the shot. 
     In the first embodiment, providing lead shot with a mechanically and chemically bound inert polymer coating, shot prepared according to this method may be used. Conventionally prepared shot can simply be overcoated with a polymer coating, either including a solvent or solventless. Preferred polymers include fluorinated polymers such as TEFLON (polytetraflouroethylene) and related polyfluoro compounds offering superior performance values. These include using enhanced polymers, where the polymer either includes a secondary resin or includes a resin primer to improve adhesion. The coated shot is then embedded in a medium which provides uniform support to maintain the spherical shape of the shot, even if the shot itself becomes molten. A variety of substances can be used to provide the support beds. Preferably among support bed materials are casting compounds, fine silica or glass beads, gels, columns of air, and similar materials. The shot is raised to a temperature above the melting or deformation point of the shot itself. This allows the polymer to be heated to the temperature required to optimally cure and bond the polymer with deformation occurring to the lead shot. Additionally, as the molten shot with the baked polymer is allowed to cool, which cooling can be accelerated by air exchange, there is an opportunity for mechanical bonding at the lad-polymer interface. In the alternative, to prepare the coated shot, the atmosphere of the shot tower is provided with an aerosol fog of polymer. These aerosols are prepared according to conventional methods and do not constitute an aspect of this invention, per se. The molten lead droplets, as they exit the sieve fall through the fog and are coated with the polymer. The intrinsic heat of the molten droplets bonds the polymer to the shot as it is formed at the temperature required to optimally cure and bond the polymer. Additionally, as the molten droplets cool, there is an opportunity for mechanical bonding at the lead-polymer interface. The coated process can be enhanced by utilizing electrostatic spraying and coating techniques. This process has the advantage of coating the shot without introduction of separate processing steps. Thus, the shot is insulated from the environment, with an inert polymer which resists peeling or erosion. The shot is raised to a temperature above the melting point of the shot itself. As the shot is allowed to cool, which cooling can be accelerated by air exchange, mechanical and chemical bonding of the coating to the shot, as well as baking of the coating, is secured. Thus, the shot is insulated from the environment, with an inert polymer which resists peeling or erosion. 
     To demonstrate the superior safety and lead leaching-resistance of the inventive shot, a series of comparisons were made, preparing shot coated with TEFLON available from duPont and similar fluorinated polymer available from Whitford under the name Whitford 1014, a resin enhanced fluorinated polymer, compared according to conventional procedures which call for baking of the polymer at 400° F. for 20 minutes, as opposed to higher temperatures, as reflected in the graphs following. The shot so prepared was subjected to a variation of the standardized test for erosion rate, prescribed by Regulation, 50 CFR 20.134 (C) specifically referencing Kimball et al, Journal of Wildlife Management 35 (2), 360-365 (1971). Specifically, pursuant to the regulations identified, hydrochloric acid is added to each capped test tube in a volume and concentration that will erode a single No. 4 lead shot at a minimum rate of 5 mg/day. Test tubes, each containing either conventional lead shot or the inventive shot, are placed in a water bath on a stirring hot plate. A TEFLON coated magnet is added to each test tube, and the hot plate is set at 42° C. and 500 rpm. Erosion of shot is determined on a daily basis for 14 consecutive days by analyzing the digestion solution with an atomic absorption spectrophotometer. The shot are all weighted at the end of the 14-day period to confirm cumulative weight loss. The 14-day procedure is repeated. Specific statistical analysis are required by the regulation. This variation is actually more severe than that prescribed by regulation. 
     As demonstrated by the foregoing comparative data, shot coated with an inert polymer according to the claimed invention exhibits superior erosion characteristics releasing substantially reduced amounts of lead, under standardized testing. 
     
         __________________________________________________________________________gr5-1 -DuPont coating using conventional curing at maximumconventional temperature - 400 F. for 20 min.day     control shot          gr5-1-1                gr5-1-2                      gr5-1-3                            gr5-1-4                                  gr5-1-5__________________________________________________________________________1       899.2  610   647.8 775.3 569.3 7842       814.9  852.1 763.3 879.3 733.2 897.83       763.5  748   719   727.5 711   7714       533.3  549.7 615.4 626.5 551.1 479.65       709.9  735.1 747.9 736.3 776.8 785.46       791.6  779.9 840.1 671.6 806.3 748.17       666.9  776.5 719.9 641.7 741.1 821.58       711.1  731.9 755.9 775.6 795   763.29       918.2  833   878   661.5 862.8 802.910      774.4  838   892.4 836   867   817.811      706.4  780.5 849.1 791.5 840.6 898.112      791.4  924   878.3 695.9 901.6 851.313      764.6  831.7 860.9 463   687.1 72314      600.1  822.9 791.8 813.7 900.2 892.3total ppm   10445.5          10813.3                10959.8                      10295.4                            10743.1                                  11036.0pct. of control          103.521                104.924                      98.563                            102.849                                  105.653mean pct.                  103.102median pct.                103.521__________________________________________________________________________ 
    
     
         ______________________________________gr1-1 -DuPont coating using embedded curing at temperatureabove conventional - 400 F. for 20 min. then 625 F. for 20 min.(control ppm is projected and is believed to be low)    controlday      shot    gr1-1-1 gr1-1-2                          gr1-1-3                                gr1-1-4                                      gr1-1-5______________________________________ 7       --      4.2     1.7   3.1   5.8   12 9       --      10      7     8     33    5211       --      4.1     4.3   3.9   21.2  46.914       --      5       4     13    58    92total ppm    5000.0  23.3    17.0  28.0  118.0 202.9pct. of          0.466   0.340 0.560 2.360 4.058controlmean pct.                      1.557median pct.                    0.56______________________________________ 
    
     
         ______________________________________gr4-1 -DuPont coating using embedded curing at temperatureabove conventional - 400 F. for 20 min. then 625 F. for 20 min.day        control shot                 gr4-1-1  gr4-1-2                                 gr4-1-3______________________________________ 2         717        16       8      12 4         670        23.4     13.2   14.5 7         690        37       25     25 8         508.4      17.3     16     14.4 9         509.4      16.9     15.2   11.710         509        12.9     12.7   11.511         551.6      18.7     19.3   19.512         361.2      13.7     14.6   14.413         287.6      16       15     16.414         208        15.3     14.4   14.4total ppm  5012.2     187.2    153.4  153.8pct. of control       3.735    3.061  3.069mean pct.                      3.288median pct.                    3.069______________________________________ 
    
     
         ______________________________________gr4-2 -DuPont coating using embedded curing at temperatureabove conventional - 400 F. for 20 min. then 625 F. for 20 min.day        control shot                 gr4-2-1  gr4-2-2                                 gr4-2-3______________________________________ 2         720        6        3      15 4         686        4.3      1.8    14.4 7         690        3        2      28 8         390.1      2        2.3    12.5 9         382.8      2.2      1.3    1310         381.9      1.3      1.7    1111         656.3      1.9      3.7    1612         586.5      0.6      2      9.613         775.2      3        4      1414         611.7      0.9      1.6    11.4total ppm  5880.5     25.2     23.4   144.9pct. of control       0.429    0.398  2.464mean pct.                      1.097median pct.                    0.429______________________________________ 
    
     
         __________________________________________________________________________px4-1 - whitford coating using conventional curing at maximumconventional temperature - 400 degree F. for 30 min.day     control shot          px4-1-1               px4-1-2                     px4-1-3                           px4-1-4                                 px4-1-5__________________________________________________________________________ 1      831.2  194.2               696.1 385.3 697.9 424.1 2      814.6  712.1               823.5 829.9 847.7 766.5 3      861.2  806.2               785.9 842.3 819.3 859.7 4      771.6  783  704.6 753.6 691.8 731.4 5      704.8  817.8               759.8 731.1 820.4 810 6      640.8  714.2               647.3 766.5 758.7 673.2 7      772.6  777.5               761.1 551.6 786.7 770.5 8      718.6  480.8               758.6 552.9 498.1 803.3 9      957.8  455.3               984   937.8 483.3 441.810      806.1  406.6               915.3 805.9 879.7 85611      1065   423.1               886.9 847.2 944.6 869.712      812.4  631.4               975   885.7 942.1 938.813      869.2  515.9               1021  1026  977.7 861.214      679.3  764.1               947.6 894.1 660.8 735.9total ppm   11305.2          8482.2               11666.6                     10789.9                           10808.8                                 10542.1pct. of control          75.029               103.197                     95.442                           95.609                                 93.250mean pct.           92.505median pct.         95.442__________________________________________________________________________ 
    
     
         ______________________________________px1-1 - whitford coating using conventional curing at maximumconventional temperature - 400 degree F. for 30 min.day       control shot                px1-1-1  px1-1-2 px1-1-3______________________________________ 1        706.3      0.7      0.6     0 2        865.5      114.5    15.4    6.2 3        1250       270.8    31.3    7 4        745.4      689.3    157.4   20.5 5        734.1      616      182.4   31.3 6        457.4      699.9    275.7   55.6 7        600.8      711.2    478.7   111.4 8        666.7      680.8    524.6   179.3 9        599.2      648.1    624.6   207.910        582.9      682.9    680     31611        660.9      692.5    606.4   434.112        654.2      789.7    778.5   767.513        936        931.9    922.1   915.814        598        598      705.2   593.1total ppm 10057.4    8126.3   5982.9  3645.7pct. of control      80.799   59.488  36.249mean pct.                     58.845median pct.                   59.488______________________________________ 
    
     
         __________________________________________________________________________px1-2 - whitford coating using conventional curing at maximumconventional temperature - 400 degree F. for 30 min.day     control shot          px1-2-1                px1-2-2                      px1-2-3                            px1-2-4                                 px1-2-5__________________________________________________________________________ 1      1070   218   129.6 101.4 2.1  9.9 2      1140   467   258.4 431.5 5.4  12.5 3      1050   1122  933.6 1140  18.6 235.3 4      1068   1050  691.6 1150  27.3 1000 5      1023   1048  1067  1056  99.1 943.6 6      1115   1170  992.2 1133  214.2                                 1035 7      1100   1013  989.7 1032  360  1020 8      1040   1075  1050  1065  487.7                                 976.9 9      1170   1114  1109  1050  1025 113710      1050   1144  1080  1036  1042 105811      1094   1111  1096  1093  1004 112912      1130   1048  1121  1170  1092 110413      1015   824.5 758   1073  1010 728.714      964.3  904.1 955.1 953.7 915.8                                 933.9total ppm   15029.3          13308.6                12231.2                      13484.6                            7303.2                                 11323.8pct. of control          88.551                81.382                      89.722                            48.593                                 75.345mean pct.            86.552median pct.          81.382__________________________________________________________________________ 
    
     
         ______________________________________px3-1 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 10 min. then 625 F. for 6 min.day        control shot                 px3-1-1  px3-1-2                                 px3-1-3______________________________________ 1         736.3      0        0      0 2         821.7      0        0      0 3         1450       1.5      1.2    4.1 4         678.9      0.2      0      7.5 5         818.9      0        0      4.7 6         663.6      0.3      0      6.2 7         683.9      0        0      11.6 8         606.4      0        0      11 9         616.6      0        0      1210         674.1      0        0      24.811         748.1      0        0      28.612         631        1.7      0      51.313         871.7      10.4     0.8    107.514         730.6      13.5     4.6    245.3total ppm  10731.8    27.600   6.600  514.600pct. of control       0.257    0.061  4.795mean pct.                      1.705median pct.                    0.257______________________________________ 
    
     
         ______________________________________px3-3 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 10 min. then 625 F. for 6 min.day        control shot                 px3-3-1  px3-3-2                                 px3-3-3______________________________________ 1         900.6      0        0      0 2         729.1      0        13.8   0 3         704.9      0        16.8   0 4         714.5      0        18.6   0 5         715.3      0        21.5   0 6         684.3      0.5      24.5   0 7         752.2      2        23.9   0 8         627.8      5.7      40.8   0.3 9         848.4      9.8      52.2   1810         1050       8.5      66.4   16.111         946.5      7.7      87.7   13.612         826.7      4.3      21.8   8.913         971.8      5.6      228.6  20.614         938.1      3.1      193.1  12.5total ppm  11410.7    47.2     809.7  90.0pct. of control       0.414    7.096  0.789mean pct.                      2.766median pct.                    0.789______________________________________ 
    
     
         ______________________________________px6-1 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 10 min. then 625 F. for 6 min.day        control shot                 px6-1-1  px6-1-2                                 px6-1-3______________________________________ 1         775.2      0        0      0.5 2         611.7      0        3.5    1 3         740.1      0        11.6   0.7 4         714.1      0        20.3   1.7 5         706.2      0        26.1   8.9 6         584.9      0        28.8   19.1 7         904.7      0        42     10.1 8         939        0        35.9   14.4 9         747.7      0        52.6   20.110         844.1      0.3      52.3   13.611         614.3      0.9      82.3   19.112         715.6      1.7      136.9  21.213         744.7      1.1      204.4  20.714         718.8      3.2      282.3  29.9total ppm  10361.1    7.2      979.0  181.0pct. of control       0.069    9.449  1.747mean pct.                      3.755median pct.                    1.747______________________________________ 
    
     
         ______________________________________px7-2 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 10 min. then 700 F. for 3 min.day        control shot                 px7-2-1  px7-2-2                                 px7-2-3______________________________________ 1         714.1      0.9      3.2    0 2         706.2      2.6      11.3   0 3         584.9      1.9      13.3   0 4         904.7      3.2      12.5   0 5         939        16.7     18.2   0.2 6         747.7      18.9     18.7   0 7         844.1      15.6     18.1   0 8         614.3      14.3     18.7   0.1 9         715.6      30.7     17.5   010         744.7      33.7     20.5   0.111         718.8      20.1     25.1   0.112         653.4      27       29.9   0.513         720.2      23.3     24.5   0.414         706.7      26.5     23.2   26.3total ppm  10314.4    235.4    254.7  27.7pct. of control       2.282    2.469  0.269mean pct.                      1.673median pct.                    2.282______________________________________ 
    
     
         ______________________________________px7-3 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 10 min. then 700 F. for 3 min.  controlday    shot      px7-3-1 px7-3-2                          px7-3-3                                px7-3-4                                      px7-3-5______________________________________ 1     669.2     2.5     0     0     0.3   0 2     843.6     2.2     0.4   0     0.3   0 3     945.3     10.2    0.8   0     4.3   0 4     1088      15.6    2     0.5   6.6   0 5     539.8     20.6    3.3   1.4   7     0 6     981.9     51.7    2     0.9   9.8   0 7     1025      32.2    48.6  3.3   8.4   0.1 8     1038      34.6    19.4  1.5   10.7  6.6 9     982.3     34.5    31.2  19.1  12.9  8.610     1010      44.1    38.1  20    16.7  15.611     769.1     42.3    39.8  8.5   14.8  9.812     1400      45.8    45.5  10.5  13.7  14.913     1211      46.1    57.1  9.3   11.8  18.814     994.7     54.1    99.7  10    16.2  27.8total ppm  13497.9   436.5   387.9 85.0  133.5 102.2pct. of          3.234   2.874 0.630 0.989 0.757controlmean pct.                1.697median                   0.989pct.______________________________________ 
    
     
         ______________________________________px8-1 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 30 min.day        control shot                 px8-1-1  px8-1-2                                 px8-1-3______________________________________ 1         640.7      0        3      0.4 2         724.3      0.1      7.5    0 3         731.6      0        6.3    4.1 4         770.5      0        32.8   7 5         964.7      0        84.3   6.3 6         667.1      2.4      153.5  7.1 7         713.3      0.4      130.7  11.2 8         726.1      0.2      178.8  9.3 9         674.9      13       210.3  16.210         809.7      12.4     175.9  21.711         826.9      21       247.1  48.912         686        16.8     277.7  53.613         653.7      15.1     263.8  55.814         722        13.8     307.3  72.4total ppm  10311.5    95.2     2079.0 314.0pct. of control       0.923    20.162 3.045mean pct.                      8.043median pct.                    3.045______________________________________ 
    
     
         ______________________________________px8-2 - whitford coating using embedded curing at temperatureabove conventional - 450 F. for 30 min.  controlday    shot      px8-2-1 px8-2-2                          px8-2-3                                px8-2-4                                      px8-2-5______________________________________ 1     599.8     0       0     2.1   0     1.9 2     905.2     0       0     9.9   0     3.5 3     912.7     0       0     18.9  3.2   11.2 4     1014      0       0     29.9  2.2   13.6 5     534.5     0       0     25.9  2.5   10 6     1095      1.4     0.1   65.3  16.1  22.9 7     658.6     0.3     0.1   52.8  13.1  14.4 8     626.1     0.3     0.3   72.8  18.9  23.9 9     985.2     0.5     0.2   82.2  17.4  32.610     1050      0.6     0.2   89.4  26.1  35.811     945.4     0.4     0.5   108.6 36.6  49.612     1160      4.6     2.4   119.3 27.6  49.613     1099      6.8     10.4  135.3 37.9  69.814     977.9     34.5    44.6  167.3 35.3  94.1total ppm  12563.4   49.4    58.8  979.7 236.9 441.3pct. of          0.393   0.468 7.798 1.886 3.513controlmean pct.                2.812median                   1.886pct.______________________________________ 
    
     In alternative embodiments, lead is replaced as an element of the shot. In a first alternative, a core of a relatively dense metal, i.e., a metal with a specific gravity greater than that of lead, greater than 11.35, is overcoated with a less dense metal, which is not environmentally toxic. Among the metals that exhibit a specific gravity above 11.35, only uranium dep. and tungsten present realistic alternatives. The remaining alternatives are set forth in the following Table. 
     
         ______________________________________METALS WITH SPECIFIC GRAVITY GREATERTHAN LEAD - 11.35             Speci-  Melt- Rare  Ra-             fic     ing   or    dio             Grav-   Point Pre-  ac-  Pyro-Metal    Symbol   ity     C.    cious tive phoric______________________________________Americium    Am       13.67    994  yes   yes  noCurium   Cm       13.51   1340  yes   yes  noGold     Au       19.32   1064  yes   no   noHafnium  Hf       13.31   2227  yes   no   yesIridium  Ir       22.42   2410  yes   no   no39rcury  Hg       13.55    liquid   no      noNeptunium    Np       20.25    640  yes   yes  noOsmium   Os       22.57   3045  toxic no   noPalladium    Pd       12.02   1552  yes   no   noPlatinum Pt       21.45   1772  yes   no   noPlutonium    Pu       19.84    641  yes   yes  noProtactinium    Pa       15.37   1600  yes   yes  noRhenium  zre      21.02   3180  yes   no   noRhodium  Rh       12.41   1966  yes   no   noRuthenium    Ru       12.41   2310  yes   no   noTantalum Ta       16.65   2996  yes   no   noTechnetium    Tc       11.5    2172  yes   yes  noThallium Tl       11.85    303  yes   no   noThorium  Th       11.72   1750  yes   yes  noTungsten W        19.3    3410  no    no   noUranium  U(dep.)  18.95   1132  no    no   yes(dep.)______________________________________ 
    
     Among metals having a lower specific density than lead for use as metals that may be provided as the outer coating about the W or U dep. core are zinc, bismuth, aluminum, tin, copper, nickel, iron or alloys made thereof. The proportion of core to coating will vary on the density of the metal forming the outer coating. If using tungsten as an example, if bismuth is selected, the tungsten will constitute 16.3% of the shot, while tungsten will constitute 52.1% (by weight) if the outer coating is formed of aluminum. As the core materials have extremely high melting points, 3410° C. for tungsten and 1132° C. for depleted uranium, the cores can be coated by conventional coating techniques, using metal or metal alloy baths, as described. 
     In a second non-lead containing alternative, the relatively light metals and alloys thereof described above are prepared in a molten bath and a powder of either W or U dep. is introduced thereto, creating a suspension of the denser metal in the lighter molten metal. This molten suspension may be formed into concentric spheres, again by a variety of methods, but most preferably, dropping through conventional shot towers, as lead shot is currently produced. Again, relative weights of the lighter and denser metals should be selected to give an average specific gravity equal to that of lead. In this respect, it should be known that selection of softer metals, such as tin, will give improved acceptability, although alloys made from any of the above-identified metals or the metals themselves, will be softer than the steel shot of the prior art. 
     This invention has been disclosed in terms of general descriptions, as well as reference to specific examples. Modifications and alternatives, particularly with regard to the identity of the chemically resistant polymer, ratios of metals, etc., will occur to those of ordinary skill in the art without the exercise of inventive faculty. These alternatives remain within the scope of the invention, save as excluded by the limitations of the claims appended hereto.