MXPA99000651A - Environmentally safe projectable targets - Google Patents

Abstract

A shooting activity and a clay target (10) which can be formed without pitch for use in such activity is provided. The activity involves shooting shot (50) at the target (10) and breaking targets hit by the shot. The target can be formed with a binder and filler and cast into a strong yet brittle state. Targets in accordance with the invention should be substantially pitch free and have a high LD 50 toxicity level as well as high frangibility. This can be accomplished in accordance with the invention by forming the targets with high internal stresses such as are formed by forming targets in unstable crystal states.

Description

WHITE PROJECTABLE TO ENVIRONMENTALLY SAFE This application claims the priority of United States Serial No. 08 / 857,813, filed on May 16, 1997.

BACKGROUND OF THE INVENTION The invention relates generally to a new composition of the material for the use of a projectile, frangible and friable object and more particularly to a rifle shooting activity such as target shooting or against mobile ceramic targets with a target environmentally acceptable. The appearance of a typical target, also known as a "plate," which can be used for clay pigeon shooting or moving ceramic targets, is shown as white 10 in FIGS. 1 -3. In use, the target 10 is commonly launched from a launching device or unloader 20 at a high speed and generally flies away from the shooter 30, armed with a rifle 40. The shooter 30 points the rifle 40 towards the flying target 10 and fires a pattern of bullets or pellets 50 from the rifle 40 towards the target 10 in order to impact and fragment the target 10. Therefore, to increase the amusement of the shooter 30, the target 10 must be sufficiently frangible and friable so that it will fragment when hit by a relatively low number of pellets 50. With respect to non-fragmented and impacted targets by at least one pellet, as a general rule, it is desirable for less than approximately 10% of those targets to have been impacted by three or more pellets. In the best targets, this percentage will be less than 4%. White 10 must also be able to be smoked, that is, reduced to a cloud of dust or small fragments, when it is impacted by a considerable number of pellets 50. It is extremely frustrating for shooters, if they hit target 10, but white 10 does not break, or if they make a perfect shot at white 10 and white only breaks into a relatively small number of pieces, without providing the "smoky" effect. In general, at least approximately 80% of the broken targets from the shot must be broken into five or more pieces when hit by experienced shooters long enough to break more than 98% of the pitch targets on which they shoot. With the best targets, this broken percentage in 5 or more pieces will be approximately 90%. In addition to being easily fragmented, the target 10 must be firm enough to remain intact, despite being subjected to considerable force by the launcher 20. When leaving a discharger, the target is traveling in a common manner at the top speed of approximately 147.2 km per hour. A target is unacceptable if even around 2% is broken when it is launched. Target 10 must also be firm enough to be stacked in a box, pushed during transportation, have a long storage life when subjected to a wide range of environmental conditions and that is relatively inexpensive. In case of not being satisfactory if even approximately 2% of the targets are broken when stored for 45 days and this number must be less than 1% for whites of the highest quality. A standard commercial target for target shooting or against moving ceramic targets is formed with tar pitch or coal tar, together with fillers such as clay, finely divided minerals and the like. An example of a widely used and well received conventional white is sold under the WHITE FLYER brand. Said white is mainly formed of petroleum pitch and limestone powder. The white weighs approximately 95 grams. It is approximately 10.79 cm in diameter and approximately 2.84 cm in height. Shooting or against mobile ceramic targets is usually done outdoors. Therefore, when conventional tar targets are fragmented and fall to the ground, they can cause several environmental concerns, for example, there is a concern that if they are ingested by an animal, the sharp edges of a broken target or the materials of a White constion will cause internal problems to the animal. Also, it may appear scattered on the ground and the petroleum base of the tar has caused some environmental concern.

Over the years, the purposes for producing clay targets with lower environmental risks have been made, for example, U.S. Patent No. 3,884,470 describes a white made from sulfur and various additives. German Patent No. 24 39 247 discloses a white made with sulfur, filler and plasticizer such as styrene. U.S. Patent No. 4,623,150 describes a white made from filler and binder, in which the ingredients are mixed with solvent, packaged in the form of a blank and the solvent is extracted. U.S. Patent No. 3,840,232 describes the targets with sulfur and limestone dust and describes the use of clay additives. International Publication No. WO 94/09339 describes the use of various fillers such as sulfur and gypsum. Canadian Patent No. 959203 and German Patent No. 22 54 725 also disclose pitch-free targets. The contents of each of these patents is incorporated herein by reference. The targets formed according to these patents have not proved satisfactory and to date, a tar-free target has not been accepted in the market. Some of the tar-free whites are too strong, that is, they do not break even when they are hit with a relatively large number of pellets. For example, a target sold by I. F.O. of Aura, Finland is rarely fragmented, even when hit with a perfect shot. Some of the pitch-free whites break-when they are thrown by the unloader or develop cracks when stored for several months. Some are too plastic, that is, they are not easily removed from a mold, nor maintain their shape, nor break when impacted with a relatively large number of pellets. Accordingly, it is desirable to provide an improved target that overcomes the disadvantages of the prior art.

BRIEF DESCRIPTION OF THE INVENTION Generally speaking, according to the invention, a shooting activity and a target that can be formed without pitch for use in said activity are provided. The activity involves shooting bullets in a target and breaking the targets hit by the shot. While some targets will be impacted by at least one pellet and remain unbroken, less than 25% of the unbroken targets impacted by one or more pellets will have been hit by three or more pellets. Whites will also break consistently in 5 or more pieces when hit by several pellets. The white can be formed with a binder and a filling and emptying in a firm but fragile state. When the sulfur is selected as the binder, the blank preferably includes a sulfur modifier, such as lignin sulfonate. Fillers include limestone powder, clays and other inert solid powders. Other materials To improve the properties of targets, such as degradation promoters and flame retardants can also be included. The targets according to the invention must be essentially free of pitch and have a 50 LD toxicity level of more than 15 g / kg as well as high frangibility. This can, according to the invention, form the targets with high internal stresses such as are formed by the formation of targets in unstable crystal states. A preferred method of blanching is to heat the ingredients to a temperature above which the structure of the material changes (160 ° C in the case of sulfur), maintaining such temperature for a prolonged period of time to effect such a change (preferably about one hour in the case of sulfur) and then emptying the targets below this temperature, (such as a temperature of 132.2 ° C) to produce a target in an unstable physical state, which will fragment upon impact. As a result, targets that have LD 50 levels considered to be at least 20 times higher than what can be achieved with conventional tar targets. Accordingly, it is an object of the invention to provide an improved friable target. Another object of the invention is to provide a friable target that is substantially free of pitch.

A further object of the invention is to provide a tar-free target having the characteristics of flight and fragmentation of a conventional pitch target. Even another object of the invention is to provide a firing activity that will cause less environmental risks. Even a further object of the invention is to provide an improved method of forming friable targets. Even other objects and advantages of the invention will be obvious in part and in part will be apparent from the specification and the drawings. Accordingly, the invention comprises the different steps and the relationship of one or more of said steps with respect to the others, and the article having the characteristics, properties and the relation of elements, which are exemplified in the following detailed description, and the The scope of the invention will be indicated in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the invention, reference is made to the following description, taken in relation to the attached drawings, in which: Fig. 1 is a perspective view of a shooter dedicated to a shooting activity in which the Shooting pellets are fired at a friable flying target; Fig. 2 is a side view of the blank of FIG. 1; and Fig. 3 is a plan view of the blank of Fig. 1.

DETAILED DESCRIPTION OF THE PREFERI DAS MODALITIES The invention relates to a shooting activity that has a reduced environmental impact through the use of targets that can be made substantially free of pitch; can be stored for prolonged periods under adverse weather conditions; and they can even break when hit by a number of firing pellets. For example, in preferred embodiments of the invention where a whole target was hit by at least one pellet, well below approximately 10% and more desirably below 5% of those targets will have to be struck by three or more pellets fired from a rifle and they will remain unbroken. This information can be obtained by executing the shooting activity with a conventional unloader, and firing at a distance of 24.57 meters with 12-gauge rifles. The targets that do not break are visually inspected later by cracks or bags formed by the blow of the pellets, but they do not break the targets. In addition, blanks according to the preferred embodiments of the invention will be broken into five or more pieces more than 805 times when they are sufficiently struck by experienced shooters to break approximately 98% of the targets they fire. When inexperienced shooters execute the shooting activity according to the invention, many of the broken targets will be hit with "poor" shots and the results are less reproducible. The blanks according to the preferred embodiments of the invention must be formed in a friable and frangible state and may lack pitch or other environmentally undesirable ingredients. The following ingredients are advantageously included in a blank formed according to the preferred embodiments of the invention. The binders, and in particular the sulfur, are advantageously included in the targets of the invention. The binder must be strong enough to maintain the integrity of the target, although sufficiently unstable to break easily under appropriate conditions. Other binders include various resins, waxes, glycosides, starches, sugars, ureas, and thermoplastics that are capable of exhibiting friable or brittle properties. It is preferred to avoid environmentally undesirable binders. The sulfur is preferably included at about 35-45%, more preferably 40-42% of the mixture. As used herein, the percentages of composition are based on weight. Fillers are advantageously added to the composition of the blank. The fillers are inert, solids, are not significantly hygroscopic and are environmentally acceptable. Calcium carbonate (limestone) especially in a finely ground form has proven to be a preferred filler. Other fillers include plasters, sands, sands, ash dust, glass, metal sulphates, non-metallic sulfates, igneous, sedimentary or metamorphic rocks ground, metal oxides and silicates. Limestone is readily available in most parts of the world and is economical compared to many other fillers, such as metered sand and calcium sulfonate. It has also been shown that calcium carbonate is not only environmentally safe, but promotes the neutralization of acids that can be produced by the reactions between sulfur in the blanks and compounds in the field. In fact, it has been found that the application of a combination of calcium carbonate and sulfur powder to plants can lead to several beneficial effects. Calcium carbonate can be included in approximately 30 to 60% of the target with variable results. Using approximately 50%, considerable cost effectiveness is achieved, while still providing a product with a manageable consistency and a final product of adequate weight and density. The deviation of more than 1 to 2% from 50% in certain compositions involving a sulfur binder can lead to significant loss of strength, flowability, mixing ability, weight and friability of the target. The modifiers are also advantageously included in the blanks according to the invention to improve the molding properties as well as the brittleness of the finished product. For example, when sulfur is used as a binder, the lignin sulfonate is advantageously added, on a preferred scale from about 2% to 8%, more preferably about 5% by weight of the added sulfur, or about 1%. % up to 4% and more preferably, about 2% by weight of the mixture. The degradation promoters are also desirable. Even if the target is environmentally benign, fragments of a broken target can be sharpened and cause internal injuries if swallowed by an animal. Broken targets that are scattered in a field may also be out of sight. Accordingly, it is desirable to include a degradation promoter, such as a clay that expands in water, which expedites the degradation of the targets used. The degradation promoters, such as water-expandable clays, particularly alumina silicate (bentonite clay) can also serve as a mixing aid to improve the uniformity of the material during mixing and emptying. The degradation promoter (alumina silicate) is advantageously included as 2 to 4% by weight of the mixture.

The insufficient degradation promoter does not tend to produce the desired effect of uniformity of mixing and environmental separation. The excess degradation promoter is expensive, can lead to premature degradation of the fine product during storage and less fragile, more uniform targets. The excess degradation promoter can also affect the structure of the target, such as conduction to cracks formed by the release of internal stresses. Fire-proof agents are advantageously included in the target. For example, if a target includes sulfur and fragments of the target in a field are exposed to fire, such as in a brush fire, or the burning of a store that stores the targets, it is desirable to prevent the target from igniting and releasing air the sulfur that contains gases. A particularly suitable flame suppressant is polyvinyl chloride (PVC). The addition of 2 to 10%, preferably 4 to 9% of fire suppressant (PVC) is advantageous. PVC is included by mixing the PVC powder with other ingredients before casting. PVC is degradable by ultraviolet light and bacteria that are present in nature. Flow additives are also advantageously included in the target mixture. Magnesium stearate, in particular from about 0.5% by weight of the white mixture will improve the flowability of the mixture and acts as a lubricant to improve the lubrication of the blanks emptied from the molds. Including less magnesium stearate may not lead to the desired properties and using more than 0.5% magnesium stearate is expensive and may not lead to significantly improved properties. However, using more than about 0.25% will be adequate for some applications. Pigments, such as carbon black, can be used to impart a desired appearance to the target. The addition of carbon black can also lead in some way to improved flow rheology. It has been found that the use of approximately 0.12% is adequate. The finished product can also be painted to change its appearance. For example, a fluorescent orange color can be applied to the upper part of it. Also, several known flame retardant paints, such as latex flame retardant paints, can help to render the product unable to withstand combustibility therein. Although the mechanism for forming friable targets is not completely understood, it is considered to refer to the ability to empty targets in an unstable manner. For example, sulfur is an S8 molecule and is normally connected in a ring shape. It is considered that by heating the sulfur, it is possible to open the ring to form a chain of sulfur atoms. It is considered that continuous heating binds the chains to form sulfur "polymer" or "oligomer" chains in the heated state. This is evidenced by a change in viscosity above the sulfur melting point from a temperature of 160 ° C to 187.7 ° C. While the depleted sulfur is initially a monoclinic crystalline structure, the stable state of the sulfur below 95 ° C is rhombic. Rhombic sulfur has a structure similar to disintegrated gypsum. As the monoclinic sulfur emptied reverts to a rhombic state, the accumulated stresses and energy are released and a cracked or structurally brittle solid is produced. Therefore, it is preferable to keep as much sulfur as possible in the monoclonal state since this will maintain the internal tensions that promote brittleness, while cracking and a weak product are avoided. It is considered that if the lignin sulfonate is present when the sulfur molecules are opened during heating, the open chains of the sulfur will bind to the lignin sulfonate compound and form polymer-type compounds including lignin sulphonate and sulfur. So, the sulfur will not be able to return to rings S8 when the temperature is reduced. It is considered that by linking to open sulfur chains, lignin sulfonate is effective to avoid the monoclinic crystal structure that is formed in the initial cooling from the inversion to the rhombic structure which is more stable at reduced temperatures. It is considered that the previous actions of lignin sulfonate create tension and therefore store potential energy in the material, leading to the material having the correct balance of strength and brittleness. It is considered that if the sulfur / lignin sulfonate combination is maintained at a temperature of more than about 176.6 ° C for approximately more than one hour, a sufficient amount of "polymers" of sulfur and lignin sulfonate will be formed. It is considered that if higher temperatures or longer heating periods are employed, the material will become undesirably viscous, which will interfere with processing. If a significantly shorter time or temperature is used, it is considered that an insufficient number of sulfur rings will open and bind to the lignin sulfonate, leading to a target having lower potential energy and therefore undesirably lower friability. Preferred embodiments of the invention will be explained with reference to the following examples, which are provided for purposes of illustration only and are not intended to be considered in a limiting sense.

Example 1 A blank composed of 41% sulfur, 38% limestone powder, 9% Bentonite clay, 9% PVC, 2% lignin sulfonate and 1% magnesium stearate was prepared. First the sulfur was melted and all the ingredients were added simultaneously. The mixture was then heated to 176.6 ° C and maintained at that temperature for one hour. Subsequently, the mixture was cooled to 132.2 ° C and the blanks were emptied into conventional blank casting molds. After emptying in the saucer shape of Figs. 2-3, the upper and lower parts of the target were painted with fire retardant paint. The resulting targets had the approximate weight and feel of conventional tar targets. When hit by a hard object, they emit the familiar tinkling sound of a highly frangible object, such as a conventional white or porcelain plate. It was found that whites have an important storage life and were strong enough to be launched from a conventional unloader. In addition, targets were fragmented into numerous pieces when hit by a relatively small number of pellets fired from a conventional rifle during clay pigeon shooting or against ordinary mobile ceramic targets. The targets can not sustain combustibility on their own and they degraded into a powder relatively quickly when subjected to the environmental exposure test.

Example 2 Targets were prepared from 41% sulfur, 50% finely ground limestone powder, 3% alumina silicate 0.5% magnesium stearate, 0.12% carbon black, 4% PVC powder, and 2% lignin sulfonate (5% by weight of sulfur). The sulfur melted at a temperature of 126.6 ° C was charged with all the ingredients in suitable ratios, except for the PVC powder, under conditions of continuous mixing and maintained at that temperature. The temperature of the mixture was then raised to 176.6 ° C and retained at that temperature for one hour, with stirring, to allow the modification and composition of the ingredients. The temperature of the mixture was then reduced from 129.4 ° C to 135 ° C and the PVC powder was added under continuous mixing, until the powder was completely dispersed and the mixture was homogeneous. The molten mixture was then poured into the saucer shape of Figs. 2-3 using conventional pouring techniques and the finished product was painted with fire retardant latex paint immediately after removal from the casting machine. The resulting targets had the approximate weight and feel of conventional pitch targets. When hit by a hard object, they emit the familiar tinkling sound of a highly frangible object, such as a conventional white or porcelain plate. It was found that whites have an important storage life and were strong enough to be launched from a conventional unloader. The targets can not sustain combustibility on their own and they degraded into a powder relatively quickly when subjected to the environmental exposure test. The targets were fragmented into numerous pieces when they were hit by a relatively small number of pellets fired from a conventional rifle during clay pigeon shooting or against ordinary moving ceramic targets. Of the targets that have been hit by at least one pellet during a shooting exercise but were not broken, below 50% of these had been hit by more than two pellets. When they are fired by experienced shooters who are able to break at least 98% of the targets they shoot, more than 50% and typically more than 90% of the targets are broken by the impact on five or more pieces.

Comparative Examples In order to confirm that the targets according to the invention represent a marked improvement over the targets produced by reasonable efforts by following the teachings of several references of the prior art, an effort was made to produce targets according to the teachings of those references of the prior art. In this commitment, the exact amounts and percentages described herein were used when they were available. When the scales were given, an intermediate value was selected. As demonstrated below, the blanks produced by this effort to reproduce the prior art were orders of magnitude lower than those formed according to the invention, in terms of acceptability as substitutes for conventional tar-based blanks.

Comparative Example A Making a general reference to the Patent of the 4f United States No. 3, 884,470, a mixture containing elemental sulfur and 1% lignin sulfonate were mixed and heated to a temperature of 176.6 ° C in an electrically heated vessel under conditions of continuous mixing. Mix heated was cast in a white mold cooled with water to ° C circulating through the mold jacket and compressed for 30 ° C. The targets would not be released from the mold without ^ Additional cooling and considerable difficulty. A second cast was made, using mold release agent from lecithin and 60 seconds of compression. It took approximately two minutes to remove a blank from the mold. By increasing the molding time to 90 seconds and reducing the cooling water temperature to 4.4 ° C, the requirement of two minutes would be reached in order to remove the blanks from the water. mold. When the composition was maintained at 176.6 ° C for approximately 40 minutes, the casting was of a very plastic material that would neither be released from the surface of the mold, nor maintain its shape as a cast if released. To the extent that any targets were produced, they exhibited defects of any kind, such as cracks, scratches, elongation or complete collapse and could not be used in the target shooting or against mobile ceramic targets.

Comparative Example B Referring generally to U.S. Patent No. 3,840,232, a mixture containing 48% elemental sulfur, 48% limestone powder and 4% bentonite clay was mixed and heated in an electrically heated vessel until a temperature of 126.6 ° C. a lecithin mold release agent and a material emptying well were used with 1 1 second molding time. Although the release was good, the whites exhibited a high percentage of cracks, which formed before the removal of the targets from the die. In an effort to eliminate this problem, the cooling water was removed from the die in order to increase the temperature thereof and slow down the cooling process. Although this was of some help in eliminating the cracking problem, it did not eliminate it completely. After storing those blanks for 30 days, you-cracked and separated if they moved even slightly.

Comparative Example C Referring generally to German Patent Publication No. 2439247, a mixture containing 68% elemental sulfur, 24% white sand (70-325 standard EU mesh) was loaded into an electrically heated vessel at a temperature of 135 ° C until the sulfur melted and the sand mixed completely. Maleic acid (2%) was added and dissolved in the solution. The vapors at this point were very irritating to the eyes, nose and lungs. A styrene monomer (6%) was added at this point and mixed into the compound. Even with an exhaust hopper, the vapors were very irritating and the styrene was difficult to mix homogeneously. The mixture was loaded into a mold for 10 seconds and water was circulated at 12.7 ° C in the mold. A lecithin mold release agent was used in the die to aid in the release. However, the product was not released properly. The excess material had been scraped from the die, which had to be cleaned before casting to a second target. The second target was also impossible to eject from the die. Accordingly, six plaque samples were removed on aluminum foil in order to obtain a solid sample of the product. Even if the problems of mold release were overcome, the resulting product would not be sufficiently brittle and therefore, would not fragment adequately when struck by a relatively small number of pellets. The material produced was not suitable for clay pigeon shooting or mobile ceramic targets.

Comparative Example D Referring generally to WO 94/09939, Example 1, a mixture containing 45% elemental sulfur and 55% calcium carbonate (limestone powder or gypsum) was mixed in an electrically heated vessel at a temperature of 120 ° C. It was necessary to raise the temperature to 126.6 ° C, since the mixture at 120 ° C was too thick for emptying. The blanks were emptied with a mold temperature of 12.7 ° C and a molding time of 5 seconds. Although the blanks were well emptied, there was some cracking at the time of mold release. With this formulation and casting temperature, the solidification rate was so rapid that it was necessary to empty excessively massive blanks to maintain a sufficiently high temperature of the casting body while the mold was closed. An inspection of the product after 48 days of storage showed that 100% had cracked in the investment to the stable glass structure.

Comparative Example E Referring generally to WO 94/09939, example 4, a second mixture containing 45% elemental sulfur, 29% limestone powder and 30% white sand, the sand having a scale of size between 88% between 106 microns and 212 microns of particle size, were mixed in an electrically heated vessel at 187.7 ° C and emptied into a mold using water at a temperature of 15.5 ° C. This mixture would not be emptied adequately and empty targets would be obtained in the outer portion of the target. The mixture is fixed very quickly and does not allow complete die closing. Although the release properties were good, the fl ow capacity was poor and the mixture was very abrasive. Some of the whites began to crack in a few minutes and after 13 days, 47% exhibited visible cracks. The material was white without breakage and had an insufficient fragile quality to be used in clay pigeon shooting or against mobile ceramic targets. With respect to U.S. Patent No. 4,623, 150, the procedures described therein were followed and resulted in a blank having inadequate friability. Such targets were very difficult to break when shooting experienced shooters and the examination of whole targets showed that the targets frequently did not break when struck by as many as nine pellets. Less than 85% of whites hit by 3 or more pellets broke. Also, even when they broke, the blanks were broken into two to four pieces, instead of being fragmented into a plurality of fragments.

In view of the above, it is clear that only including the ingredients common to those established in those patents (sulfur, lignin sulphonate, alumina silicate, limestone or sand) will not produce an acceptable target, ie one that will have good drainage and will fragment consistently when hit by three or more pellets. For example, even when the target is made with: sulfur and lignin sulfonate and heated to a temperature of 176.6 ° C; sulfur, limestone and bentonite clay; sulfur, sand, limestone; or limestone, lignin sulfonate and magnesium stearate, the results are generally unsatisfactory. An explanation with respect to the unsatisfactory results of the prior art efforts may lie in the lack of a full understanding of the nature of the binder structure. For example, the ina stable crystal form of sulfur below 95 ° C is rhombic. From 95 ° C to the melting point of 15.5 ° C, the ina stable crystal form of sulfur is monoclinic. It takes a while for this transformation to take place. Although the mechanisms of the thermodynamic memory of sulfur are not fully understood, when the sulfur is heated to a temperature of 160 ° C to 176.6 ° C, the molecular structure of the sulfur changes, since the three allotropes reach a type of equilibrium state during the period maintained at this temperature. It is considered that this particular state of equilibrium of the three allotropes increases the amount of monoclinic crystals produced as the sulfur solidifies, which in turn allows a greater number of these monoclinic crystals to be modified to be unable to invert to the form Orthorhombic in its normal investment cycle. This helps produce the desired friable product. When a cooling of white cools to below 95 ° C, it will try to invert to the rhombic shape. When this inversion takes place, certain stresses and energy are released forming cracks and structurally weak solids. This is evidenced by the amount of cracked and weak targets produced by the procedure set forth in U.S. Patent No. 3,840,232 and WO 94/09939. It is therefore considered that, the use of sulfur only, without adequate modifications and process control will not lead to the production of suitable targets. Likewise, it is considered that when the sulfur is modified only with lignin sulfonate at a temperature of 176.6 ° C for a period, it results in an unprocesable product, as evidenced by the product made by the United States Patent No. 3,884,470 .

Example 4 To demonstrate the exceptional performance of the targets formed in accordance with the invention, the targets according to Example 2 were fired from an unloaded and shot with a .12 caliber rifle firing lead bullets at a distance of 24.57 meters. Fragmentation results were compared with those of conventional pitch targets in Table 1 below.

Table 1 WHITE TEST RESULTS IMPACTED AT 24.57 METERS BRAKE STRAP EXAMPLE 2 A 46/50 44/50 48/50 46/49 B 42/50 43/50 44/50 41/50 C 43/50 46/50 44 / 50 45/50 D 48/50 44/50 47/50 49/49 E 47/50 46/50 45/50 47/50 TOTALS 449 of 500 456 of 498 89.8% broken 91.6% broken COLLECTION OF RESULTS OF WHITE NOT BROKEN NO. OF BRANDS OF PELLA BREA EXAMPLE 2 0 13 10 1 6 7 2 5 3 3 4 0 4 1 1 5 2 0 6 0 0 7 1 0 8 0 0 9 0 0 10 0 0 As is evident from table 1, the blanks formed in accordance with the invention improved the yield of the high quality tar targets and exhibited results that were orders of magnitude higher than those that would result from firing on the blanks of the Comparative Examples. It should be noted that of the 1 1 unbroken targets of example 2 recovered that had been hit by at least one pellet, only one had been hit by more than three pellets. Likewise, more than 84% of the targets in Example 2 that were hit and broken broke into 5 or more pieces. Therefore, the results of breaking the targets of Example 2 are at least as good as those of a conventional pitch target. It will be noted, therefore, that the previously established objects, among those that became apparent from the above description, are efficiently achieved and, since certain changes can be made by carrying out the above method and in the established article without departing of the spirit and scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings should be construed as illustrative and not in a limiting sense. It is also understood that the following claims are intended to cover all the generic and specific characteristics of the invention described herein and all the declarations of the scope of the invention that should be included therein.

Particularly it should be understood that in said claims, the ingredients or compounds cited in the singular will be understood to include compatible mixtures of such ingredients wherever the sense permits.

Claims (40)

1. CLAIMS 1 . A suitable target for target shooting or against mobile ceramic targets, comprising: approximately 35% to 45% sulfur; about 30% up to 60% fill; and about 1% up to 4% sulfur modifier; where the white is in the state produced by heating the white ingredients, including the sulfur, the filler and the sulfur modifier to a temperature of more than about 160 ° C, to cool the material to a temperature between about 1 15.5 ° C and 160 ° C and empty the material in a target; The target of claim 1, wherein the target materials are in the achieved state by keeping the ingredients melted at a temperature of about 176.6 ° C for about one hour and then emptying at a temperature of 132.2 ° C. 3. The target of claim 1, wherein the sulfur is added to about 40% to 42% of the target material. 4. The blank of claim 1, wherein the filler is selected from the group consisting of gypsum, sands, clays, ash dust, glass, metal sulfates, non-metallic sulfates, igneous rock, sedimentary or ground metamorphic, metal oxides and silicates. 5. The blank of claim 1, wherein the filler consists essentially of calcium carbonate. The blank of claim 1, which includes about 40% to 42% sulfur and about 49-51% calcium carbonate. The blank of claim 1, wherein the sulfur modifying component comprises lignin sulfonate. The blank of claim 1, wherein the lignin sulfonate is added to the materials on a scale from about 2% up to 8% of the weight of the added sulfur. The blank of claim 6, wherein the blank includes about 2% lignin sulfonate. 10. The blank of claim 1, including 2% up to 4% degradation promoter. 11. The blank of claim 1, which includes about 2% to 4% aluminum silicate. 12. The blank of claim 1, wherein about 2% to 10% PVC is added to the target ingredients. 13. The blank of claim 6, wherein about 4% to 9% PVC is added to the target ingredients. The target of claim 6, wherein the blank is cast and at least one fire retardant paint application is applied to at least a portion of the blank cast. 15. A target suitable for clay pigeon shooting or against moving ceramic targets, comprising binder and filler cast in a state of fragility and sufficient dimensions, so that when shot with bullets from a twelve-caliber rifle from a distance of 24.57 meters by shooters sufficiently skilled to impact approximately 98% of the targets if they fire from that distance, less than approximately 10% of the entire targets hit by at least one pellet will have been hit by three or more pellets and will remain intact; the target having a LD 50 toxicity level greater than 15 g / kg. 16. The target of claim 15, wherein the target has sufficient friability so that less than about 5% of whole targets hit by at least one pellet are struck by three or more pellets and remain intact. The target of claim 15, wherein the targets are sufficiently fragile to break into five or more pieces more than about 80% of the time when they are impacted by shooters experienced enough to impact approximately 98% of the targets they hit. shoot with twelve-caliber rifle bullets from a distance of 24.57 meters. The target of claim 16, wherein the targets are broken into five or more pieces more than about 80% of the time when they are hit by sharpshooters skilled enough to impact approximately 98% of the targets they fire with bullets from 12 caliber rifles from a distance of 24.57 meters. 19. The target of claim 15, where the white's brittleness is such that when the white is hit hard with a metal bar, the white will emit an established tinkling sound. The blank of claim 15, wherein the blank has substantially the weight and dimensions of a conventional clay blank. 21. The blank of claim 15, which includes about 35% to 45% sulfur. 22. The blank of claim 15, which includes about 40% to 42% sulfur. 23. The target of claim 22, which includes about 1% up to 4% lignin sulfonate. 24. The target of claim 23, in the state achieved by heating the materials to a temperature of about 176.6 ° C for one hour, then emptying to about 132.2 ° C. 25. The target of claim 15, which substantially does not contain pitch. 26. The target of claim 18, which includes about 40% to 42% sulfur. 27. The blank of claim 15, which includes about-2% to 10% PVC. 28. The blank of claim 15, including 2% up to 4% degradation promoter. 29. The blank of claim 15, in the state achieved by heating the materials to a temperature of about 176.6 ° C for one hour, then emptying to about 132.2 ° C. 30. A method of forming a friable object, comprising: preparing a composition, including sulfur, filler and sulfur modifier, heating the composition to a temperature above 160 ° C; cool the composition to a temperature below 132.2 ° C and empty the blanks at that temperature. 31 The method of claim 30, wherein the composition includes about 1% up to 4% lignin sulfonate. 32. The method of claim 31, wherein the composition includes about 40% up to 42% sulfur. The method of claim 30, wherein the composition is heated to a temperature of about 176.6 ° C for about one hour, and drained at a temperature between about 129.4 ° C and 135 ° C. 34. The method of claim 33, wherein the PVC powder is added to the composition at 129.4 ° C to 135 ° C under mixing conditions. 35. The method of claim 34, including the step of painting the blank cast with the fire retardant paint. 36. The method of claim 30, wherein the composition is maintained at a temperature of about 160 ° C for an effective amount of time to effect sufficient entanglement between the sulfur materials to increase the viscosity of the molten material. 37. The method of claim 30, wherein the sulfur is at least partially converted to and maintained in a monoclinic state. 38. The method of claim 30, which includes the step of substantially excluding any pitch from the target composition. 39. The method of claim 30, including the step of maintaining a plurality of blanks in a box for 45 days and not developing cracks in more than 2% of the blanks. 40. A shooting activity, comprising the steps of: providing a plurality of targets having an LD 50 of 15 g / kg or more; throw the targets in the air and shoot the targets with a rifle; breaking the targets impacted by the pellets, to the extent that less than 4% of the entire targets hit by at least one pellet were hit by three pellets or more. SUMMARY A firing activity and a clay target (10) are provided which may be formed without pitch for use in such activity. The activity involves firing the shot (50) at the target (10) and breaking the targets hit by the shot. The white may be formed with a binder and filler and cast in a firm but brittle state. The targets according to the invention are substantially free of pitch and have a high level of LD50 toxicity as well as high frangibility. This can be achieved in accordance with the invention by forming blanks with high internal stresses such as those formed by forming blanks in unstable crystal states.