Improved projectile

Abstract

An improved formulation and process for a projectile, such as a paintball used in the sport of paintball is provided. The improved formulation comprises a fill material for a projectile such as a paintball, and a shell material. The fill material may comprise a stable mixture of a liquid, solid particles, and a gas. The shell material may comprise a mineral filler. Methods of making the foregoing are also provided.

Description

IMPROVED PROJECTILEPRIORITY CLAIM

[0001] The present application claims priority to U.S. Provisional Patent Application No. 63 / 507,572, the entire contents of which are incorporated by reference as if fully set forth herein.FIELD

[0002] The invention relates to improved projectiles, methods of making them, and methods of using them. In particular, in aspects if the invention, the invention relates to improved projectiles for use in the sport of paintball, referred to as paintballs.BACKGROUND

[0003] Paintballs are types of projectiles, or ammunition, used in the sport of paintball, and are currently generally comprised of a spherical shell made of gelatin and plasticizers like glycerol and sorbitol. The shell surrounds a fill or filler or fill material (sometimes also referred to in the sport as a “paint” or “dye”) that is capable of forming a “splatter” mark when the shell breaks on impact. The main ingredient in the fill is usually a non-toxic liquid drawn from the vegetable oil group, or the group of liquid polyethylene glycols (PEG XXX where XXX is the average molecular wt.). Thickeners, opacifiers and colourants are usually added. Glycerin and water may also be added to balance concentration gradients between the fill and the shell. Solid particles such as vegetable starches, or clays or other mineral have been added to reduce cost and increase the weight of the ball.

[0004] There are 4 commercially available liquid PEGs: PEG 200, PEG 300, PEG 400 and PEG 600. PEGs with molecular wt. less than or equal to 200 are known to diffuse readily through a gelatin shell, which causes unsightly sweating on the outside of the ball, while PEG 600 has a freezing point of 17 to 22°C and is a slush or a solid at room temperature. PEG 400 freezes at about -2°C, and PEG 300 freezes at about -7°C. None of the PEGs can be used safely in paintballs intended for use in winter conditions. This problem has been dealt with in the past by using low pour-point vegetable oils such as soybean oil which can be used to -12°C. Soy oil has two serious drawbacks: when exposed to sunlight, it can polymerize to agum that is very difficult to remove. Also, when it decays, it encourages mold growth leading to unsightly black stains which are also difficult if not impossible to remove without damaging the substrate or without using harmful chemicals. Other non-toxic fluids with low freezing points are known: polypropylene glycol 425(PPG 425) is very expensive and proprietary. Also, glycereth 10 is very expensive and causes extreme brittleness in the shell.

[0005] The PEG fluid in the paintballs can restrict water uptake by plants on or adjacent to paintball playing fields, and has been known to cause browning or dieback of grass etc.

[0006] Starch can be added to a paintball shell. However, it is known that adding 1 % by weight of starch to the gelatin shell of a paintball causes it to become extremely brittle.

[0007] Solid fillers have been added to paintball fill to lower cost. When the filler is denser than the liquid carrier fluid, it will also increase the weight of the ball. Heavier balls are known to be more accurate, but the paintball industry has imposed a safety limit of 3.5 grams per ball, which limits the cost savings achievable with solid fillers.

[0008] Titanium dioxide is used in paintballs because it is by far the best opacifier available today. It has not been practical to replace it without a loss in performance.

[0009] There is therefore the need for an improved projectile such as for use as a paintball in the sport of paintball, having improved characteristics.SUMMARY

[0010] In an aspect, the invention relates to a stable paintball that contains gas bubbles in the fill.

[0011] In an aspect, the invention relates to reduction of fraction of PEG in a paintball.

[0012] In an aspect, the invention relates to reduction or elimination of TiO2 in a paintball.

[0013] In an aspect, the invention relates to a paintball fill based on PEG 300 that does not freeze at -20°C.

[0014] In an aspect, the invention relates to a method of easily preparing a stable dispersion of gas bubbles and solid particles and calcium acetate in PEG.

[0015] In an aspect, the invention relates to a use of gas bubbles in the fill to reduce the tendency of a paintball to break at low temperature.

[0016] In an aspect, the invention relates to addition of solid fillers to the gelatin shell of a paintball without causing a large change in breakage rate.

[0017] In an aspect, the invention relates to addition of fillers to the gelatin shell of a paintball to increase hardness of the shell at a given humidity.

[0018] In an aspect, the invention relates to a clear gel made without heat by adding calcium acetate to PEG.

[0019] In an aspect, the invention relates to a paintball fill material comprising a stable mixture of liquid including at least one of carrier fluid, a rheology modifier, a primary surfactant, and a secondary surfactant.

[0020] In an aspect, the invention relates to a paintball fill material comprising (1) a stable mixture of liquid including at least one of carrier fluid, a rheology modifier, a primary surfactant, and a secondary surfactant, and at least one of (2) a freezing point depressant; (3) solid particles, and (4) one or more gasses.

[0021] In an aspect, the invention relates to a paintball comprising a shell filled with the paintball fill material comprising a stable mixture of liquid including at least one of carrier fluid, a rheology modifier, a primary surfactant, and a secondary surfactant.

[0022] In an aspect, the invention relates to a paintball comprising a shell filled with the paintball fill material comprising a stable mixture of liquid including at least one of carrier fluid, a rheology modifier, a primary surfactant, and a secondary surfactant, and at least one of (2) a freezing point depressant; (3) solid particles, and (4) one or more gasses; and optionally where the shell comprises talc or other mineral filler.

[0023] In an aspect, the invention relates to a method of making a paintball fill material.

[0024] In an aspect, the invention relates to a method of making a paintball.

[0025] In an aspect, the invention relates to a paintball shell comprising talc or other mineral filler.DETAILED DESCRIPTION OF EMBODIMENTS

[0026] Certain terminology is used in the following description for convenience only and is not limiting. The words “a” and “one,” as used in the claims and in the corresponding portions of the specification, are defined as including one or more of the referenced item unless specifically stated otherwise. The phrase “at least one” followed by a list of two or more items, such as “A, B, or C” or “A, B, and C,” means any individual one of A, B, or C as well as any combination thereof.

[0027] An embodiment includes a paintball comprising a shell and a fill material including a stable mixture of liquid, solid particles, and one or more gasses, where the fill material is contained in the shell. The one or more gasses may be small gas bubbles. An embodiment includes a fill material comprising a stable mixture of liquid, solid particles, and a gas. The stable mixture of liquid may comprise a carrier fluid, a rheology modifier, and a primary surfactant. The stable mixture of liquid may further comprise a secondary surfactant. An embodiment comprises a paintball comprising a shell and fill material comprising carrier fluid, where the fill material is contained in the shell. An embodiment comprises a fill material comprising a carrier fluid.

[0028] A combination of high density solid fillers and small evenly dispersed gas bubbles may deliver a cost reduction without exceeding a safety limit per paintball. Currently, the industry sets a safety limit of 3.5g per ball.

[0029] The carrier fluid may comprise a mixture of at least one of: water, alcohols, polyols, propylene glycol, polypropylene glycol, polyethylene glycols, polybutylene glycols, polyglycerols, ethoxylated derivatives of alcohols or polyols, any vegetable oil, including modified vegetable oils, any mineral oil or liquid petroleum derivative or any liquid made by a combination of biologically and mineral sourced materials. The carrier fluid may comprise at least one of PEG 200, PEG 300, PEG 350, glyceryl ethoxylate 10 in PEG 300, polypropylene glycol 425 in PEG 300, phenoxyethanol in PEG 300, 3-methoxy-3-methyl-1 -butanol in PEG 300, and PEG 200 in PEG 300. The amount of carrier fluid may be from 30 to 100 % by weight of the fill. The amount of carrier fluid may be from 30 to 100 % by volume of the fill. The amount of carrier fluid may be 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, or 70, 71 ,72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, or 100 % by weight, orin a range between any two of the foregoing. The carrier fluid may further comprise glycerol. Glycerol may contribute to carrier fluid mass, may influence rheology and has a role in foam stability. Glycerol may also control the brittleness of the shell.

[0030] The rheology modifier may prevent settling or creaming of particles or bubbles suspended in the carrier fluid. The rheology modifier may be at least one of the following non-limiting examples: partially crosslinked acrylic thickeners (e.g., Pemulen™ TR-1 , a crosslinked copolymer of acrylic acid and a hydrophobic C10- 30 alkyl acrylate co-monomer), thickeners based on clay (e.g., organophilic phyllosilicates, for example, Garamite 1958 from Byk), anionic surfactants (e.g., a modified acrylic, for example, Dynamon SR) or quaternary surfactants (e.g., cetearyl alcohol with behentrimonium methosulfate), or higher molecular weight polyethylene glycols (e.g., PEG 4000), gellants (e.g., calcium acetate), amorphous silica (e.g., 500 LS from Ludox), fatty acid soaps, specialty polyamides (e.g., polyamide LP3 from Croda), or specialty polyurethanes (e.g., Optiflo 2157 from Byk). The concentrations of rheology modifier may be 0.1 to 9% by weight of the total liquid phase. The concentrations of rheology modifier may be 0.1 , 1 , 2, 3, 4, 5, 6 or 9% by weight of the total liquid phase, or in a range between any two of the foregoing. In a preferred embodiment, the maximum concentration of rheology modifier is 9%. The rheology modifier may be calcium acetate. The calcium acetate may be in a concentration of 0.1 to 6% by weight of the total liquid phase. The concentration of calcium acetate may be 0.1 , 1 , 2, 4, 5, 6 or 9% by weight of the total liquid phase, or in a range between any two of the foregoing. In a preferred embodiment, the maximum concentration of calcium acetate is 9%.

[0031] The primary surfactant may allow formation of stable micro gas bubbles, and may be anionic (e.g., sodium dodecyl sulfate), cationic, zwitterionic (e.g., lauryldimethylamine oxide), or nonionic (e.g., C12E4, tetraethylene glycol monododecyl ether). The primary surfactant may be sodium laureth-2 sulfate (SLES). The amount of primary surfactant may be 0, 1 , 2, or 3% based on total weight of the fill, or from 0 to 3%, 1 to 3%, 2 to 3%, 0 to 2%, 1 to 2%, or 0 to 1 % based on total weight of the fill. However, the amount of primary surfactant may exceed this amount.

[0032] The secondary surfactant may boost and stabilize the action of the primary surfactant, and may also be selected from anionic or cationic or zwitterionic or nonionic groups. The secondary surfactant may be Cocam idopropyl betaine. Thesecondary surfactant may be in an amount from 0 to 1 % based on total weight of the fill, or in a range between any two of 0.1 , 0.5 or 1 % of the total weight of the fill. However, the amount of secondary surfactant may exceed this amount.

[0033] The primary and secondary surfactants may also be referred to as a foaming agent.

[0034] The solid particles, also referred to as solid weighting agent, may have a size range from .1 to 100 microns. The solid particles may comprise at least one of titanium dioxide, aluminum oxide, zinc oxide, barium sulphate, calcium sulphate, iron oxide, amorphous silica, barium titanate, wollastonite, calcium carbonate, specialty pigments, recycled glass, sand, native starch and modified starches, talc, clays and modified clays. The amount of solid particles may be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, or 64% by weight, or in a range between any two of the foregoing. The amount of solid particles may be 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, or 35 % by volume (calculated), or in a range between any two of the foregoing. These solid particles may allow reduction or elimination of TiC>2 as a weighting agent. Titanium dioxide is used in paintballs because it is by far the best opacifier available today. However, it is a suspected carcinogen and its use is now restricted. Until now, it has not been practical to replace it without a loss in performance. However, the combined scattering effect of many tiny gas bubbles and an increased concentration of solid filler particles allows paintballs with satisfactory marking power without the use of titanium dioxide.

[0035] One or more gasses which may include any gasses that are non-toxic and inert at room temperature and pressure including but not limited to nitrogen, air, carbon dioxide, helium, argon and all the noble gasses. The amount of air may be 0 to 41 .9% by volume. The amount of air may be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , or 41.9% by volume, or in a range between any two of the foregoing. Gas bubbles have not been heretofore added to the fill.

[0036] The stable mixture of liquid may further comprise a freezing point depressant. The freezing point depressant may comprise at least one of calcium acetate, glyceryl ethoxylate 10, polypropylene glycol 425, 1 ,3 propanediol, 3-methoxy-3-m ethyl- 1 -butanol, dipropylene glycol, dimethyl sulfoxide, or PEG 200. A small amount of calcium acetate mono hydrate (hereinafter calcium acetate or CaAc), as described herein, can reduce the freezing point of PEG 300 to -20°C. The freezing point depressant may be at a concentration of 0.5% to 10% by weight of the liquid phase of the fill. The freezing point depressant may be at a concentration of 0.5, 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of the liquid phase of the fill, or in a range between any two of the foregoing. In a preferred embodiment, the minimum concentration of the freezing point depressant is 0.5% by weight of the liquid phase of the fill.

[0037] An embodiment comprises a method for preparation of the fill. The method may comprise blending the liquid and ingredients together followed by addition of the solid particles under low shear. This step may comprise simple stirring in an open vessel. This step may comprise dispersing the foaming agents into a portion of the carrier fluid using a high speed vertical mixer like the Ystral before adding this sub-mixture to the main open vessel. The method may comprise stirring solid particles into the main open vessel to obtain a coarse slurry. Some gas bubbles may be formed by the air entrained during addition of the solid particles to the liquid. The method may comprise high shear mixing to fully disperse the solid particles and any entrained air. High shear can be obtained by passing the mixture through a mill comprised of a rotor turning at high rpm in close proximity to a stator such as the Ross mill type of in-line mixers. The method may comprise adding further, air, another gas or gasses, collectively referred to as “gas.” The amount of gas may be controlled by dispensing it from a pre-weighed container, or it may simply be added until a desired density has been achieved. Gas may be added to the fill in an open vessel by arranging any high-speed mixing shaft so that air is entrained at the same time as the fluid is being mixed. A preferred method comprises pumping the mixture through the high speed Ross mill and injecting the gas into the pipe containing the flowing slurry mixture just before the intake of the high-shear in-line mixer such as the Ross machine described above.

[0038] An embodiment comprises a shell for a paintball, which may be a shell containing a paintball fill material herein. A shell may comprise gelatin, water and at least one plasticizer. The plasticizer may range from 5 to 25% and gelatin from 35 to 55% and water from 35 to 50% of the total weight of the composition used to make the shell of the paintball. After the paintball is formed, this shell dries so thatthe % water decreases and the %of plasticizer and gelatin increase. The at least one plasticizer may be at least one of glycerin, mannitol, non-crystallizing sorbitol, propylene glycol, 1 ,3 propanediol, maltitol, sucrose, fructose, cellulose, disodium sulfosuccinate, triethyl citrate, tributyl citrate, xylitol, isomerized sugar, polyglycerol, glucose syrups, and sugar alcohol. The shell may further comprise solid particles, such as mineral fillers. That is, the shell may further comprise at least one of talc or other mineral fillers. Examples of mineral fillers include, but are not limited to, calcium carbonate, kaolin, silica, talc, clay, mica, wollastonite, glass beads, or alumina trihydrate. Fine talc can be added to the shell without substantially changing the brittleness. This not only reduces cost, but it may have benefits such as making the shell harder and thus more resistant to deformation at a given level of humidity. The amount of talc or other mineral filler may be 1-7% by weight of the total shell mixture. The amount of talc or other mineral filler may be 0, 1 , 2, 3, 4, 5, 6, or 7% by weight of the total shell mixture, or in a range between any two of the foregoing. The amount of talc or other mineral filler may be greater than 7% by weight of the total shell mixture. The amount of talc or other mineral filler may be 1-40% by weight of the total shell mixture. The amount of talc or other mineral filler may be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 34, 35, 36, 37, 38, 39, or 40% by weight of the total shell mixture, or in a range between any two of the foregoing. The amount of talc or other mineral filler may be greater than 7% by weight of the total shell mixture.

[0039] An embodiment comprises a method of a making the paintball. The method may comprise encapsulating any paintball fill material herein with any shell herein. The skilled artisan will readily appreciate methods of encapsulating fill material in a shell. For example, the preparation of soft gelatin capsules is described in Lachman, Theory and Practice of Industrial Pharmacy, Lea & Febiger, Philadelphia, Second Edition, 1986, which is incorporated herein by reference as if fully set forth.

[0040] Further embodiments herein may be formed by supplementing an embodiment with one or more element from any one or more other embodiment herein, and / or substituting one or more element from one embodiment with one or more element from one or more other embodiment herein.

[0041] Examples

[0042] The following non-limiting examples are provided to illustrate particular embodiments. The embodiments throughout may be supplemented with one or more detail from one or more example below, and / or one or more element from an embodiment may be substituted with one or more detail from one or more example below.

[0043] Reduction of % PEG 300 or PEG 400

[0044] Embodiments herein may reduce the amount of PEG fluid per ball, which in turn may reduce plant stress.

[0045] Example 1. Standard Paintball Fill Density= 1.32 g / cc. Final Weight of ,68cal ball = 3.4 g

[0046] Example 2. Foamed Paintball Fill Density= 1.32 g / cc. Final Weight of ,68cal ball = 3.4 g

[0047] Freezing Point Depressant for PEG 300

[0048] The calcium acetate in example 3 causes instant gelation of PEG type fluids. It can only be incorporated as follows:

[0049] Combine the first 5 ingredients in a stirred open vessel. Pump this slurry through an in-line high shear mixer while slowly introducing a solution of calcium acetate in glycerol and water just ahead of the intake of the high shear mixer. Once all of the calcium acetate solution has been added, switch to injection of compressed air at the intake of the high shear mixer. Continue to add compressed air until the desired density has been achieved. This example is designed to give a paintball that is robust enough to be used at -10°C. Calcium acetate prevents the fill from freezing to -20°C whereas pure PEG 300 will freeze at -7°C. Foaming the fill to a density of 1 ,2g / cc reduces the mass and therefore the energy of impact, and the foam itself allows more “give” than an incompressible liquid fill. Satisfactory marking is achieved without the use of TiC>2.

[0050] Example s Foamed Low Temp Paintball Fill Density= 1.20 g / cc. FinalWeight of ,68cal ball = 3.2 g

[0051] An alternative method may be used to make a low freezing point foamed paintball fill by creating calcium acetate and CO2 in situ through the reaction of acetic acid with calcium carbonate as shown in example 4. Part A is mixed and then added to the combined ingredients in Part B.

[0052] Example 4 Foamed Low Temp Paintball Fill Density= 1 ,24g / cc. Final Weight of ,68cal ball =3.3g.

[0053] Viscosity = 12,760 cp at 10 rpm with #5 spindle, shows trace flow behaviour, remains liquid at -20°C.

[0054] As table 5 shows, many liquids with low freezing points are miscible with PEG 300. However, none confer the resistance to freezing provided by calcium acetate.X)055] Table 5 Effect of Cooling to -20°C

[0056] The concentration of calcium acetate is best given as a percentage of the total liquid phase. The useful amount of CaAc varies from 0.1 % to 5% by weight of the total liquid phase.

[0057] Calcium Acetate also gives a clear gel when used without solid particles as in example 6 where the first 3 ingredients are blended to make a clear solution which is then gradually added to PEG 300 under high shear.

[0058] Example 6 Clear Gel, Vise = 9000 CP

[0059] Weighting Agents and Maximum % Gas

[0060] Example 7 shows how gas bubbles can compensate for the use of very high loading of high density fillers.

[0061] Example 7 Foamed Fill Density= 1 ,26g / cc. Final Weight of ,68cal ball= 3.3 g

[0062] Brookfield Viscosity with #63 spindle at 1 rpm = 213,600 cp

[0063] Brookfield Viscosity with #63 spindle at 2 rpm = 124,000 cp

[0064] The viscosity of this fill is beyond the capabilities of conventional mixing and encapsulating equipment. However, it shows strong shear thinning behaviour which makes it suitable for use as a paintball fill because it will splatter on impact. It could be made and formed into a paintball by specialized equipment known to those experienced in the art.

[0065] Example 8 Foamed Fill with Soya Oil Density= 1.08 g / cc. FinalWeight of 68cal ball = 3.0 g

[0066] The concentration of solid weighting agent may vary from zero to 64% by weight. The concentration of gas may vary from zero to 41 .9% by volume. The useful range for surfactant 1 is from zero to 3%, although excess may be added without changing the final result. The useful range for surfactant 2 is from zero to 1%, although excess may be added without changing the final result.

[0067] Addition of Filler to Gelatin Shell

[0068] Example 9 shows the recipe for the gelatin shell of a paintball, and how that can affect the impact strength.

[0069] Example 9 Solid Fillers in the Gelatin Shell vs Breakage Rate

[0070] *Balls dropped onto a smooth concrete surface from a height of 6 feet.

[0071] Addition of a relatively large amount of talc has little effect on the breakage rate. This may be due to the smaller particle size of the fine talc (<10 microns) vs the 20 to 40 micron starch particles.

[0072] One of the drawbacks of current paintballs is that they rapidly absorb moisture form the air and can become too soft to perform properly when the humidity rises above 55%, which is common in many areas. A solid filler in the shell may increase the hardness of the shell at a given humidity.

[0073] All of the above fills can be made into paintballs by encapsulating them in a shell made of gelatin, water and one or more plasticizers selected from the group consisting of: glycerin, mannitol, non-crystallizing sorbitol, propylene glycol, 1 ,3 propanediol, maltitol, sucrose, fructose, cellulose, disodium sulfosuccinate, triethyl citrate, tributyl citrate, xylitol, isomerized sugar, polyglycerol, glucose syrups, and sugar alcohol.

[0074] It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but is intended to cover all modifications which are within the spirit and scope of the invention as defined by the appended claims; and the above description. It is understood that many modifications, substitutions, and additions may be made which are within the intended spirit and scope of theinvention. The present invention is not to be limited to the specific embodiments described, as variations in the design methodologies, sizes, ratings and characteristics, applications, and other variations are contemplated.

Claims

CLAIMSWhat is claimed is:

1. A paintball comprising: a shell; and a fill material contained in the shell, the fill material comprising a stable mixture of a liquid, solid particles, and a gas.

2. The paintball of claim 1 , wherein the gas comprises gas bubbles.

3. The paintball of claim 1 , wherein the stable mixture of liquid comprises a carrier fluid, a rheology modifier, and a primary surfactant.

4. The paintball of claim 3, wherein the stable mixture of liquid further comprises a secondary surfactant.

5. The paintball of claim 1 , wherein the fill further comprises a freezing point depressant.

6. The paintball of claim 1 , wherein the fill material is based on PEG 300, and wherein the fill material does not freeze at -20 degrees C.

7. The paintball of claim 1 , wherein the gas comprises an inert gas.

8. The paintball of claim 1 , wherein the gas comprises air.

9. The paintball of claim 1 , wherein the shell comprises gelatin, water and one or more plasticizers selected from the group consisting of: glycerin, mannitol, non crystallizing sorbitol, propylene glycol, 1 ,3 propanediol, maltitol, sucrose, fructose, cellulose, disodium sulfosuccinate, triethyl citrate, tributyl citrate, xylitol, isomerized sugar, polyglycerol, glucose syrups, and sugar alcohol, or combinations thereof.

10. The paintball of claim 9, wherein the shell comprises a mineral filler.

11. A method of making a paintball, comprising filling a shell with a fill material comprising a stable mixture of a liquid, solid particles, and a gas.

12. The method of claim 11 , wherein the gas comprises gas bubbles.

13. The method of claim 11 , wherein the stable mixture of liquid comprises a carrier fluid, a rheology modifier, and a primary surfactant.

14. The method of claim 13, wherein the stable mixture of liquid further comprises a secondary surfactant.

15. The method of claim 11 , wherein the fill further comprises a freezing point depressant.

16. The method of claim 11 , wherein the fill material is based on PEG 300, and wherein the fill material does not freeze at -20 degrees C.

17. The method of claim 11 , wherein the gas comprises an inert gas.

18. The method of claim 11 , wherein the gas comprises air.

19. The method of claim 11 , wherein the shell comprises gelatin, water and one or more plasticizers selected from the group consisting of: glycerin, mannitol, non crystallizing sorbitol, propylene glycol, 1 ,3 propanediol, maltitol, sucrose, fructose, cellulose, disodium sulfosuccinate, triethyl citrate, tributyl citrate, xylitol, isomerized sugar, polyglycerol, glucose syrups, and sugar alcohol.

20. The method of claim 19, wherein the shell comprises a mineral filler.

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