WO2018132917A1 - Simultaneous irradiation and milling system - Google Patents

Abstract

An apparatus used for simultaneously milling and irradiating a material to be ground. The apparatus has a milling vessel configured to receive a material to be ground and a grinding material, the milling vessel comprising at least a radiation transparent portion; and a radiation vessel comprising a radiation compartment shaped to receive a radiation source, wherein the radiation compartment is configured to position the received radiation source such that radiation produced by the radiation source irradiates the material to be ground via the at least a radiation transparent portion of the milling vessel.

Description

SIMULTANEOUS IRRADIATION AND MILLING SYSTEM

[001] The present application claims priority from U.S. provisional application number 62/447,980 with a filing date of January 19, 2017.

Technical Field

[002] The disclosure relates to the field of milling for grinding, dispersing, and reacting substances.

Background

[003] Ball mills are used to reduce solids to small particles, or to disperse solids in a liquid, or to screen for new materials, or to perform structural and chemical transformations known as mechanochemistry. There are several types of ball mills that are based on different architectures and operating principles, including roller mills, gravity mills, oscillatory (vibratory/shaker), and attrition mills. The shaker ball mills (oscillatory/vibratory mills) operate by oscillating a hollow, usually cylindrical (also spherical or egg-shaped) grinding chamber (i.e., a ball milling vessel or a jar) along an arc that is parallel to its horizontal axis. The material that is to be ground, or dispersed in a liquid, or used for materials screening, or for mechanochemical reactions is introduced into the ball mill vessel along with grinding media (milling media), such as grinding balls, milling balls, rocks, sand, or pebbles, for example. As the hollow cylindrical shell moves back and forth on the arc path, the grinding media perform complex motions that are a combination of sliding and collisions (with vessel walls, with the material being milled, or with other milling media particles) and pulverize and mix the material in the vessel. The material being milled can be one or more distinct solids, it can contain a liquid, and can even include a gas.

[004] Ball mill systems use milling/grinding media made from different grinding materials to pulverize the solids or to disperse the solids in a liquid, or to perform mechanochemical reactions, or to screen for new materials. The material from which the grinding media are made from can include metal, rubber, ceramic, plastic, Teflon, glass balls, inorganic materials such as flint pebbles, composite materials based on inorganic compounds, such as tungsten carbide, or any combination of these. As the ball mill vessel oscillates (shakes), collisions and shear involving milling media result in grinding/milling of the material in the mill into a fine powder, and/or physicochemical transformations such as melting, eutectic formation, introduction of defects, structural rearrangements, and chemical reactions.

[005] Photochemical reactions are caused by absorption of ultraviolet, visible, infrared, or other types of electromagnetic radiation, depending upon the electronic transition in the reactant material. As light is absorbed by chemical substances in the reactant materials, the materials are elevated to a state of higher energy. Photochemical transitions can access high energy intermediates that cannot be generated thermally, thereby overcoming large activation barriers in a short period of time, and allowing reactions otherwise not possible by thermal processes. In a milling environment, light energy is absorbed by the sample material and provides activation energy for reactions of the material. Broadband high-power radiation, such as ultraviolet radiation, is often used to photochemically transform materials.

Summary

[006] The disclosure includes a novel integrated vessel (milling jar/capsule/container) for simultaneously performing ball milling processes (mechanochemistry) and photochemical reactions, including physical, structural and chemical transformations of materials, including but not limited to particle size reduction (comminution), alloying, amorphisation (or vitrification), and mechanochemical reactions for the synthesis or screening for inorganic materials, metal-organic materials (e.g. metal-organic frameworks and other types of compounds based on metal-ligand coordination bonds), organic solids, including pharmaceutical materials, such as cocrystals, solvates, hydrates, polymorphs, salts, and the like.

[007] One advantage of the ball milling vessel is that it offers an integrated assembly, which allows milling in the presence of a liquid or a gas, while simultaneous by irradiating the sample material.

[008] The ball milling vessel differs from conventional ball milling equipment and conventional photochemical devices as it includes a single integrated device for simultaneous milling and irradiation of a sample, while conventional milling vessels typically provide only for alternative, intermittent grinding and radiation exposure.

[009] A broad aspect is a simultaneous irradiation and milling system. The system includes a milling chamber for containing grinding media and a material to be ground, the milling chamber including a radiation transparent portion. The system includes a radiation chamber into which the milling chamber is placed. The system includes a mill that shakes, stirs or rotates the milling chamber and grinds the material to be ground with the grinding media by a shaking, stirring or rotation action. The system includes a radiation source optically coupled to the radiation chamber that simultaneously transmits irradiation that passes through the radiation transparent portion of the milling chamber and interacts with the material to be ground as the mill rotates the milling chamber and grinds the material.

[0010] In some embodiments, the system may include a power source that supplies energy to the radiation source.

[0011] In some embodiments, the milling chamber and the radiation chamber may be an integrated combined chamber.

[0012] In some embodiments, the system may include a lid that seals the milling chamber.

[0013] In some embodiments, the lid may include a radiation port through which radiation enters the milling chamber. [0014] In some embodiments, the system may include a grinding material inlet for feeding material to be ground into the milling chamber.

[0015] In some embodiments, the system may include a grinding media inlet for introducing grinding media into the milling chamber.

[0016] In some embodiments, the system may include a grinding material outlet for discharging ground or dispersed material that has been ground from the milling chamber.

[0017] In some embodiments, the grinding media may include at least one of metal, rubber, ceramic, plastic, Teflon, glass balls, flint pebbles, and tungsten carbide.

[0018] In some embodiments, the radiation source may be a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

[0019] In some embodiments, the radiation transparent portion of the milling chamber may include at least one of poly(methyl methacrylate), , polycarbonate, fiber glass, sapphire, quartz, and glass.

[0020] In some embodiments, the milling chamber may include an alloyed metal.

[0021] In some embodiments, the alloyed metal may include at least one of stainless steel, carbon steel, brass, bronze, and mixtures thereof.

[0022] In some embodiments, the milling chamber may include a base metal.

[0023] In some embodiments, the base metal may include copper, nickel, gold, silver, and mixtures thereof.

[0024] In some embodiments, the milling chamber may include a plastic.

[0025] In some embodiments, the plastic may include at least one of polycarbonate, polyetherether ketone, poly (methyl methacrylate), Teflon, and mixtures thereof.

[0026] In some embodiments, the milling chamber may include at least one of an inorganic compound and a composite material.

[0027] In some embodiments, the milling chamber may include tungsten carbide.

[0028] In some embodiments, the milling chamber may include precious metal catalysts deposited on its interior surface.

[0029] In some embodiments, the precious metal catalysts deposited on the interior surface of the milling chamber may include at least one of ruthenium, rhodium, palladium, silver, gold, platinum, iridium, and mixtures thereof.

[0030] Another broad aspect is a radiation vessel for use in a milling system comprising a grinding mill, a radiation source and a milling vessel comprising grinding material and a material to be ground. The vessel includes a first end and a second end diametrically opposite to the first end. The vessel includes an opening shaped to receive a milling vessel. The vessel includes a hollow elongated body spanning a length defined by the first end and the second end, wherein the elongated body defines a space for receiving the milling vessel, wherein the opening allows for the insertion of the milling vessel into the space through the opening. The vessel includes a radiation compartment shaped to receive a radiation source for producing radiation, wherein the radiation compartment comprises a radiation opening configured and positioned with respect to the space to allow transmission of the radiation from the radiation source to the space. The radiation vessel is shaped to be fitted to the grinding mill.

[0031] In some embodiments, the hollow elongated body may be of a cylindrical shape.

[0032] In some embodiments, the opening may be present on the second end, and the opening may be of an elliptical shape.

[0033] In some embodiments, the opening may be of a circular shape.

[0034] In some embodiments, the vessel may include a top shaped to seal the opening of the second end.

[0035] In some embodiments, the radiation compartment may be located in the top, such that the radiation source may transmit radiation to the space when the top is fitted to the opening and the radiation source is received within the radiation compartment.

[0036] In some embodiments, the radiation compartment may be connected to or integrated to the elongated body.

[0037] In some embodiments, the vessel may include the radiation source.

[0038] In some embodiments, the radiation source may be a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

[0039] In some embodiments, the vessel may include a connector for connecting to a power source and providing power to the radiation source from the power source or a power source.

[0040] In some embodiments, the vessel may include a heat sink positioned to evacuate heat produced by at least the radiation source.

[0041] Another broad aspect is a method of producing a product. The method includes providing a grinding apparatus fixed to a chamber comprising an inner space that has received a material to be ground. The method includes grinding the material to be ground while irradiating the material to be ground using a radiation source, wherein the radiation source is connected to the grinding apparatus such that radiation may travel into the inner space.

[0042] In some embodiments, the grinding apparatus may be a grinding mill, and wherein the grinding may be performed by grinding material contained in the chamber, the grinding material applying a mechanical force to the material to be ground as the chamber may be at least one of shaken, stirred and rotated by the grinding mill.

[0043] In some embodiments, the chamber that is provided may include a radiation transparent portion configured to permit radiation from outside the inner space to enter the inner space.

[0044] In some embodiments, the radiation source may be fixed to the chamber. [0045] In some embodiments, the grinding apparatus may be a twin screw extruder, and wherein the grinding may be performed by the screws of the twin screw extruder.

[0046] In some embodiments, the radiation may be used to disinfect the contents of the vessel.

[0047] In some embodiments, the irradiating may be used for a chemical reaction involving the material to be ground as a reagent.

[0048] In some embodiments, the radiation source may be a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

[0049] In some embodiments, the chamber may be integrated to the grinding apparatus.

[0050] In some embodiments, the chamber may be a vessel that is fixed to the grinding apparatus via a fastener.

[0051] In some embodiments, the method may include dissipating heat resulting from the radiation source via a heat sink.

[0052] Another broad aspect is a method of producing a final product. The method includes the method of producing a product as defined herein. The method includes transforming and/or combining said intermediary product to produce said final product.

[0053] Another broad aspect is a grinding mill for grinding and irradiating a target material. The grinding mill includes a fastener for retaining a milling vessel. The grinding mill includes a drive for causing at least one of shaking, stirring and rotating of the vessel received in the fastener. The grinding mill includes a radiation compartment configured to receive a radiation source, wherein the radiation compartment is configured to position the received radiation source so as to allow for the irradiation of the milling vessel by the radiation source when the milling vessel is retained by the fastener. The grinding mill includes a shield adapted to change from an open position to a closed position. In the open position, the shield allows access to the fastener, and in the closed position, the shield covers the milling vessel retained by the fastener, and the shield in the closed position covers the radiation source.

[0054] In some embodiments, the grinding mill may include the radiation source.

[0055] In some embodiments, the radiation source may be a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

[0056] In some embodiments, the radiation compartment may be present in the fastener.

[0057] In some embodiments, the radiation compartment may be present in the shield.

[0058] In some embodiments, the grinding mill may include circuitry configured to cause the radiation source to produce radiation when the shield is in a closed position.

[0059] In some embodiments, the grinding mill may include circuitry configured to cause the radiation source to cease producing radiation when the shield changes from the closed position to the open position. [0060] In some embodiments, the shield may be a retractable hood or a hatch.

[0061] In some embodiments, the fastener may be a clamp that is adjustable to accommodate to the width of the milling vessel.

[0062] Another broad aspect is an apparatus used for simultaneously milling and irradiating a material to be ground. The apparatus includes a milling vessel configured to receive a material to be ground and a grinding material, the milling vessel comprising at least a radiation transparent portion. The apparatus includes a radiation vessel comprising a radiation compartment shaped to receive a radiation source, wherein the radiation compartment is configured to position the received radiation source such that radiation produced by the radiation source irradiates the material to be ground via the at least a radiation transparent portion of the milling vessel.

[0063] In some embodiments, the milling vessel and the radiation vessel may be integrated, forming a single vessel with an inner space for receiving the material to be ground and the grinding material.

[0064] In some embodiments, the apparatus may include a top configured to seal the opening of the radiation vessel.

[0065] In some embodiments, the apparatus may include the radiation source.

[0066] In some embodiments, the radiation source may be a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

[0067] In some embodiments, the apparatus may include a grinding mill configured to receive at least the radiation vessel, and to at least one of shake, stir and rotate the radiation vessel, causing the material to be ground and the grinding media to be at least one of shaken, stirred and rotated.

[0068] In some embodiments, the grinding mill may be a ball mill.

[0069] In some embodiments, the milling vessel may be of a cylindrical shape.

[0070] In some embodiments, at least one base of the milling vessel may be hemispherical.

[0071] In some embodiments, the at least a radiation transparent portion may be the entire milling vessel.

[0072] In some embodiments, the at least a radiation transparent portion may be composed of at least one of poly(methyl methacrylate), polycarbonate, fiber glass, sapphire, quartz, and glass.

[0073] In some embodiments, the milling vessel may include precious metal catalysts deposited on its interior surface.

[0074] In some embodiments, the precious metal catalysts deposited on the interior surface of the milling vessel may include at least one of ruthenium, rhodium, palladium, silver, gold, platinum, iridium, and mixtures thereof. [0075] In some embodiments, the apparatus may include a heat sink to dissipate heat produced by at least the radiation source.

[0076] In some embodiments, the apparatus may include a power source.

[0077] In some embodiments, the power source may be a battery.

[0078] In some embodiments, the apparatus may include a connector to connect to a power outlet.

[0079] In some embodiments, the apparatus may include a wireless power receiver to receive power wirelessly from a source of wireless power.

[0080] In some embodiments, the apparatus may include the grinding media, wherein the grinding media may be at least one of metal, rubber, ceramic, plastic, Teflon, glass balls, flint pebbles, and tungsten carbide.

[0081] In some embodiments, the milling vessel may include an alloyed metal.

[0082] In some embodiments, the alloyed metal may be at least one of stainless steel, carbon steel, brass, bronze, and mixtures thereof.

[0083] In some embodiments, the milling vessel may include a base metal.

[0084] In some embodiments, the base metal may be copper, nickel, gold, silver, and mixtures thereof.

Brief Description of the Drawings

[0085] The invention will be better understood by way of the following detailed description of embodiments of the invention with reference to the appended drawings, in which:

[0086] Figure 1 is a drawing illustrating a prior art vortexing mixer;

[0087] Figure 2 is a drawing of a perspective view of an exemplary vibratory integrated ball milling and radiation vessel apparatus, where the milling vessel is displayed as being outside of the apparatus;

[0088] Figures 3A-3C are drawings of an exemplary vibratory integrated ball milling and radiation vessel apparatus;

[0089] Figures 4A-4B are drawings of an exemplary planetary integrated ball milling and radiation vessel apparatus;

[0090] Figures 5A is a drawing of an exemplary body of a radiation vessel usable with a grinding mill;

[0091] Figure 5B is a drawing of an exemplary top housing of an exemplary radiation vessel to be used with a grinding mill;

[0092] Figure 6 is a drawing of an exemplary radiation vessel with a fixed radiation source and a wire connected to the radiation source;

[0093] Figure 7 is a drawing of an exemplary radiation vessel with a heat sink and a top usable with a grinding mill; [0094] Figure 8 is flowchart diagram of an exemplary method of producing a product that has been simultaneously irradiated and ground; and

[0095] Figure 9 is a drawing of an exemplary grinding mill including a radiation source to simultaneously irradiate and grind a material to be ground.

Detailed Description

[0096] The ball milling and radiation apparatus eliminates many of the shortcomings of prior systems. An example of prior work involved manual grinding of a sample in air, using a mortar and pestle. After a period of manual grinding the sample would be exposed to visible or ultraviolet radiation, and then the process would be repeated over and over, usually until the photochemical reaction completed. Although this manner of mixing and exposing the material to radiation combined mechanochemistry and photochemistry, the vessels and devices did not permit the processes to be performed simultaneously, or under controlled environment of atmosphere or mechanical impact.

[0097] Other efforts to combine mechanochemistry and photochemistry included the use of vortexing mixers 150 with test tubes 155 or glass vials as shown in Fig. 1. The material to be ground 160 is placed in the test-tube, and milling media 165 (e.g., BBs) are placed in the test tube 155 on the vortexing mixer 150. The assembly (vortexing mixer 150, test tubes 155, material 160, and milling media 165) is mounted in a cupboard-like chamber 170 that includes a continuously water-cooled mercury lamp 175 as a source of broadband ultraviolet and visible radiation. Operation of the vortexing mixer 150 provides grinding, mixing, and mechanochemical reactivity. When both the mercury lamp 175 and the vortexing mixer 150 are turned on, it is possible to conduct photochemical and mechanochemical transformations, but the entire set-up is placed in a safety cabinet 180 (photoreaction cabinet) during operation. Also, this set-up provides almost no control over mechanical agitation and grinding, as it operates through simply placing a test-tube on the surface of a randomly moving vortexing mixer.

[0098] DEFINITIONS:

[0099] By "radiation vessel", also referred to herein as a radiation chamber, it is meant a vessel that receives in an inner space either a milling vessel or, when the radiation vessel and milling vessel are a single vessel, that receives directly the material to be ground and the grinding material, and that allows radiation from a source of radiation to enter the inner space through an opening of the radiation vessel (e.g. the opening may have a window that is transparent to the radiation of the radiation source). The radiation vessel may have a compartment for receiving the radiation source, where the compartment may be integrated to the radiation vessel, or included in a separate component connected or connectable to the portion of the radiation vessel with the inner space (when connected, forming the radiation vessel). [00100] By "grinding apparatus", it is meant an apparatus that is configured to grind a material contained in an inner chamber. The inner chamber may be integrated to the grinding apparatus, or connected (or connectable) to the grinding apparatus via a fastener (e.g. where the fastener may be screws, a clamp, a holder, etc.) Examples of a grinding apparatus include a grinding mill, a twin screw extruder (e.g. were the grinding is performed by the twin screws), etc.

[00101] By "grinding mill", it is meant an apparatus that is configured to grind a material contained in an inner chamber (e.g. the inner chamber integrated to the grinding mill itself, or present in a separate vessel that is fixed, connected, attached, etc., to the grinding mill) through oscillating, shaking, stirring and rotating, etc. Examples of grinding mills include ball mills, cutting mills, crusher mills, attrition mill, etc. In some examples, the grinding mill may be used when the material to be ground is to undergo a mechanochemical reaction (e.g. where the milling bodies transfer a mechanical force to the material to be ground) as the grinding mill shakes, stirs and/or rotates the material to be ground.

[00102] By "milling vessel", it is meant a vessel that is configured to contain, within an inner compartment, a material to be ground and a grinding material. When the milling vessel allows radiation to enter and irradiate the material to be ground, the milling vessel contains at least a radiation transparent portion (i.e. transparent to the radiation). In some examples, by "at least a radiation transparent portion", it includes a milling vessel that is entirely radiation transparent.

[00103] By "material to be ground", it is meant a material that is to be broken down due to the action of the grinding mill and the grinding material. By "broken down", it may involve a reduction in shape and/or size of the particles or of the material itself, the breaking of bonds on a molecular level, etc. By "broken down", it may be meant that the material may undergo a mechanochemical reaction during the grinding and/or irradiating process (where, in some examples such as with a liquid, there is no change in the size or shape of the material) where the material to be ground may be a reagent undergoing a chemical change in structure or change in chemical properties (i.e. chemical reaction) during the grinding and/or milling. In some cases, the material to be ground may be a liquid or a solution.

[00104] AN EXEMPLARY ILLUSTRATION OF A MILLING AND RADIATION APPARATUS:

[00105] As shown in Fig. 2, one example of the ball milling assembly 200 includes a milling chamber 205 (millingjar), a UV/visible light chamber 210, a UV/visible light source 215, power supply and housing 225, and control electronics 220. The milling chamber 205 includes a UV- and/or visible light-transparent portion. It will be understood that even certain examples as presented herein describe the use of ultraviolet radiation, chambers, and sources, other light spectra and their corresponding chambers, sources, and the like, can also be used. [00106] Sample material (not shown in Fig. 2) is loaded into milling chamber (or milling jar) 205, which includes a UV/visible light-transparent portion. The milling chamber 205 can be constructed of metals (such as stainless steel, structural steel, aluminum, copper, nickel, etc.), plastics (such as PMMA, PTFE, PEET, polycarbonate, etc.), composite materials (such as carbon fiber, fiber glass, etc.), glass, and other materials including those which are UV/visible light-transparent materials.

[00107] A user places mixing media (milling balls or other type of abrasive material particles) into the milling chamber (or jar) 205 with the sample material. The user seals the milling chamber 205 with a removable lid and inserts the milling chamber 205 into UV/visible light chamber 210 such that the UV- and/or visible light-transparent portion of the milling chamber 205 is in the exposure path of UV/visible light source 215. The user inserts the chamber 205 into the integrated irradiation and milling vessel 230, and the UV/visible light- source 215 and the integrated irradiation and milling vessel 230 are switched on. As outlined above, although this examplary assembly 200 irradiates the sample material with UV and/or visible electromagnetic radiation (EMR), the apparatus can be utilized to irradiate a sample with any type of EMR under simultaneous milling, such as radio, microwave, terahertz, infrared, X- rays or gamma-rays. Also, the milling chamber 205 and (UV and/or visible light) radiation chamber 210 are adaptable to other types of radiation that are not electromagnetic, using a compact source, including beta- and alpha-rays.

[00108] Figs. 3A-3C are photographs of an example vibratory UV/visible light assembly 300. Figs. 3A-3C show the system in operation with UV/visible light chamber 310, UV/visible light source 315, battery and housing 325, and the integrated irradiation and milling vessel 330. The system 300 shown in Figs. 3A-3C includes UV/visible light source 315 as an on-board battery pack, but other power sources are scaled as the size of the mill, sample, media, UV/visible light irradiation chamber, and the other system components are scaled. The power may be provided via a wired connection, or via a chip or circuitry for receiving wireless power (e.g. a wireless power receiver for receiving transmitted wireless power). For example, an industrial sized system could include a larger wired power source.

[00109] The apparatus uses defined radiation wavelengths and is not limited to broadband, high-power radiation sources. As such, the apparatus may eliminate the need for continuous cooling of the radiation source with water or other coolants as in previous systems. Additionally, the compact design and manufacture of the milling chamber 205, UV/visible light irradiation chamber 210, and the integrated irradiation and milling chamber 230 avoids the need to use a large safety enclosure, such as a photoreaction cabinet, to conduct reactions. The assembly 200 incorporates a self-powered source of radiation directly into the milling/mixing chamber 205, which is mounted on the integrated irradiation and milling device 230. For example, as shown in Fig. 2, a battery and battery housing 225 and control electronics 220 are used to control UV/visible light source 215. As such, the assembly 200 is safe to be used in a laboratory without any additional shielding.

[00110] The present disclosure is not limited in size or to a particular milling style. While Fig. 2 shows an example of a UV/visible light assembly 200 designed for a mixer/vibratory mill, the present teachings can also be used with planetary, attrition, and industrial-scale mills (such as roller mills, gravity mills, and the like).

[00111] Fig. 4 illustrates an UV/visible light assembly 400 applied to a planetary mill. A planetary assembly 400 includes a combination milling/UV/visible light chamber 450 and a lid 460. A sample material (not shown) is placed in the combination milling/UV/visible light chamber 450 along with grinding/milling media (not shown). A UV/visible light source 415 is mounted to the lid along with a UV/visible light power source 425, such as the battery pack shown in Fig. 4. Control electronics 420 control the power source 425 and UV/visible light source 415. Since the chamber is a combination milling/UV/visible light chamber 450, lid 460 includes a radiation port, such as holes 465 through which the UV/visible light radiation passes to reach the sample material placed in the milling/UV/visible light chamber 450. A groove 470 in the lid 460 accepts an O-ring 475 to seal the milling/UV/visible light chamber 450 when the lid 460 is attached.

[00112] The apparatus can be used to conduct simultaneous mixing or milling of solid, liquid, or gaseous samples, or their various combinations, under exposure to radiation.

[00113] The apparatus may use UV and visible radiation during mixing of materials that can absorb such radiation in order to undergo a chemical reaction, for example a photoreaction, including polymerizations, or a photo-activated reaction that proceeds through a different (for example radical-based) mechanism.

[00114] Examples of such photoreactions include, but are not limited to, photodimerizations, photochemical reactions, polymerization, generation of activated species, photo-induced isomerizations, photo-induced radical reactions, decarbonylation, substitution reactions, and the like.

[00115] The apparatus can be used in [2+2] photodimerizations, for example using olefins, diolefins or other chemical species that contain double bonds, or acetylenes and other chemical species containing triple bonds, or arenes and other types of chemical organic, inorganic, organometallic or metal-organic species containing extended conjugated π-electron systems, or any combination thereof.

[00116] Additionally, the apparatus can be used in photochemical reactions involving a photo-activated redox system and/or photo-activated electron transfer, such as but not limited to the reactions catalyzed by differently coordinated Ru2+/Ru3+ redox system. Likewise, the simultaneous mechanochemical and photochemical alterations can be used in polymerization of di-, tri- or in general oligoacetylenes. The apparatus can also be used in generation of activated species, such as singlet oxygen and in photo-induced isomerizations, such as cis-trans isomerizations of azobenzenes or metal complexes, or ring-opening and -closing of diarylethylenes.

[00117] Further uses of the present teachings include photo-induced radical reactions, such as homolytic bond cleavage and reactions that follow from it, as well as Norrish type I and type II reactions, as well as decarbonylation of carbonyl organic or organometallic compounds with the loss of carbon monoxide, and substitution reactions of metal complexes, for example but not limited to replacement of carbon monoxide ligands on metal carbonyl complexes.

[00118] The disclosure provides a milling system for grinding, dispersing, and reacting substances that provides simultaneous irradiation and milling/mixing of a solid, liquid, or gaseous sample, or any combination thereof.

[00119] RADIATION VESSEL:

[00120] Reference is now made to Figures 5A and 5B, illustrating an exemplary radiation vessel 500. The radiation vessel 500 may optionally include a detachable housing 510 with a radiation compartment 507 for receiving a radiation source (e.g. radiation source 521 as shown in Figure 6).

[00121] The radiation vessel 500 is configured such that it may receive in an inner space a milling vessel, the milling vessel containing, e.g., the material to be ground and the grinding material. It will be understood that in some examples, the inner space of the radiation vessel 500 may also function as a vessel for the material to be ground and the grinding material, receiving directly the material to be ground and the grinding material. The radiation vessel 500 is also adapted to receive a radiation source 521, such that radiation from the radiation source 521 may be transmitted to the inner space, irradiating the material to be ground contained therein. The radiation vessel 500 is adapted to be fastened to a grinding mill. As such, the radiation vessel 500, containing directly the material to be ground and the grinding material, or by containing the milling vessel, allows for the simultaneous grinding or milling of the material to be ground as the material to be ground is being irradiated, while the radiation vessel 500 and its contents are shaken, stirred and/or rotated.

[00122] In some embodiments, the radiation vessel 500 may be adapted to prevent ambient light from reaching its inner space (e.g. as a result of the opacity of the material used for its shell or exterior surface).

[00123] The radiation vessel 500 has a first end 502, a second end 501, where the first end 502 and the second 501 define an elongated body 503. The second end 501 may also have an opening to receive a milling vessel. The radiation vessel 500 may have an upper surface 504 for receiving the detachable housing 510, where the upper surface 504 may have a radiation opening 508 allowing for the radiation emitted by the radiation source 521, attached to the housing 510, to enter the inner space defined by the elongated body 503.

[00124] The housing 510 may have an opening 507 configured to receive the radiation source 521. There may also be an opening or channel 506 for letting a wire or cable 516, connectable to the circuitry attached to the radiation source 521, pass, so that the wire 516 may connect to a power source (e.g. connect to a power outlet). The housing 510 (and the upper surface 504) may have fastening points 517 (e.g. holes) allowing for the elongated body portion of the radiation vessel 500 to attach to the housing 510. The fastening points 517 may also be configured to further allow a heat sink 523 to be attached to the elongated body and/or the housing 510 using at least one fastener or group of fasteners 524. The housing 510 may have a contour 505 surrounding the radiation compartment 507.

[00125] The hollow elongated body 503 may be of a cylindrical shape, or any other shape adapted to accommodate the shape of the milling vessel. In some examples, the inner space of the elongated body 503 may be shaped to receive the milling vessel, where the shape of the outer surface of the elongated body 503 may be adapted to fit and remain fixed to a fastener of a grinding mill. For instance, the fastener may be a clamp, where the elongated body 503, as well as ends 501 and 502, are adapted to be fitted to the clamp (e.g. may have specific grooves or protrusions).

[00126] The radiation vessel 500 has an opening to receive the milling vessel. The opening may be present on one of the ends (501 or 502) of the elongated body 503. As shown in Figure 5A, the opening is present on end 501. In some examples, the opening may be present on the elongated body 503 itself, where e.g., there may be a flap or hatch that may open or close to position the milling vessel in the inner space of the elongated body 503. In some examples, the elongated body 503 may be composed of two halves, where the halves may be separated, producing the opening to insert the milling vessel such that the milling vessel is contained in the inner space of the elongated body 503 once the two halves of the elongated body 503 are joined.

[00127] In some embodiments, the opening of the radiation vessel 500 for receiving the milling vessel may be shaped to accommodate the milling vessel such that it may pass through the opening to be received in the inner space of the elongated body 503. When the opening is positioned on an end 501 or 502, the opening may be of a shape congruent with the area of a cross-section of the milling vessel. For instance, if the milling vessel is of a cylindrical shape, then the opening may be of a circular shape. In some examples, the opening may be of an elliptical shape. [00128] In some embodiments, such as when the radiation vessel 500 includes a housing 510 separate from the elongated body 503 for receiving the radiation source, the elongated body 503 may have a radiation opening 508 allowing for radiation produced by the radiation source 521 to enter the inner space of the radiation vessel 500. In examples where the radiation compartment 507 is connected to the elongated body 503 such that there is no separate housing 510, the radiation source 521 may be positioned in the radiation compartment 507 such that the radiation source 521 emits radiation that may travel directly into the inner space, where the radiation source 521 may be placed directly above the inner space.

[00129] Reference is made to Figure 6, illustrating a radiation source 521 received in the radiation compartment 507 of the housing 510 of the radiation vessel 500. The radiation source 521 may be additionally fixed to the radiation vessel 500 via a fastener, such as an adhesive such as a glue, a screw, bolt, clamp, etc.

[00130] The radiation source 521 may also be provided with its own circuitry, the circuitry allowing, in some examples, to control the activation or deactivation of the radiation source 521. A wire or cable 516 may be connected to circuitry of the radiation source 521, for transmitting power to the radiation source, the wire or cable 516 connected to a power source such as a power outlet. It will be understood, as shown in Figures 3B and 3C, that the radiation vessel may be configured to receive a power source (e.g. a battery; a capacitor) for providing power to the radiation source 521. It will be understood that the radiation source 521 may be interchangeable, where a different radiation source 521 may be placed in the radiation compartment 507 depending on the irradiation needed (e.g. when a specific type of radiation is necessary to trigger or to allow a mechanochemical reaction to take place; to sterilize a sample, etc.)

[00131] The radiation vessel 500 may also have a top 515 for fitting to and/or sealing the opening adapted to receive the milling vessel 205. In some examples, the radiation vessel 500 may not have a top 515, where, for instance, the clamp or the fastener of the grinding mill may seal the opening adapted to receive the milling vessel.

[00132] In some examples, as shown in Figure 7, the radiation vessel 500 may also have a heat sink 523 configured to dissipate heat produced by at least the radiation source 521.

[00133] The fastener 524 is used to fasten, in some embodiments, the housing 510 to the elongated body 503 (or its surface 504). The fastener 524 may also be used to fasten the heat sink 523 to the rest of the radiation vessel 500. Exemplary fasteners may be screws, bolts, clips, clamps, adhesives, welding attachments, etc.

[00134] METHOD OF PRODUCING A PRODUCT BY SIMULTANEOUS MILLING AND IRRADIATING: [00135] Reference is now made to Figure 8, illustrating an exemplary method 800 of producing a product that has been simultaneously milled and irradiated. It will be understood that the product produced by the exemplary method 800 may be an intermediary product, the intermediary product ultimately transformed and/or combined into the final product that is to be sold and/or shipped.

[00136] The radiation may be used as a component necessary to complete a chemical reaction, such as chemical reactions associated with radiation chemistry. For instance, the radiation may be used to destroy toxic organic compounds (e.g. irradiation to break certain organic compounds into dioxins that can then be dechlorinated). The radiation may also be used to sterilize (e.g. ultraviolet germicidal irradiation). The radiation may be used to break down or assemble polymers (e.g. such as certain plastics), where e.g. the breaking of the polymers may be furthered by the milling or grinding action.

[00137] Examples of chemical products resulting from a mechanochemical reaction, such as one achieved using a grinding apparatus (e.g. a ball mill) may be: the synthesis of an yttrium based metal (MIL-78) from YFb and trimesic acid; the synthesis of Mg(BH₄)2 by high energy reactive ball milling of MgB₂, synthesis of borasiloxane-based macrocycles; etc. For example, milling of resorcinol with l,2-trans(4-pyridyl)ethylene would yield rctt-l,2,3,4-tetrakis(4- pyridyl)cyclobutane that would then assemble with copper(II) acetate (or a range of different copper(II) carboxylates, e.g. propionate, butyrate, etc.) to form an inverted metal-organic framework (IMOF).

[00138] Moreover, an exemplary product that can be produced by the simultaneous milling and irradiation (UV-radiation) may be metal-organic frameworks (involving solid-state cocrystallization, photocatalysis and synthesis). For example, the synthesis of metal-organic frameworks may be by the mechanochemical assembly of olefin- or oligo(olefin)-based organic ligands with metal ions, forming coordination polymers or metal-organic frameworks. The addition of UV radiation or visible irradiation may allow for a photochemical reaction within the initially formed coordination polymer or metal-organic framework, yielding a new, different coordination polymer or a metal-organic framework. The reverse process is also possible, where a coordination polymer or a metalorganic framework based on metal ions and cyclobutane- based ligand is assembled mechanochemically first, and then converted to a different coordination compound or a coordination polymer or a metal-organic framework by reversal of [2+2] photodimerization using ultraviolet light.

[00139] In some examples, coordination polymers or metal-organic frameworks may be synthesized by mechanochemical milling of a metal ion source (a metal salt) and an azobenzene- based ligand in the cis- or trans-form. Activating the irradiation during milling would enable switching between the cis- or the trans-form of the ligand, leading to a different metal-organic framework or a coordination polymer.

[00140] In some examples, the exemplary process would allow for the production of coordination complexes, coordination polymers or metal-organic frameworks by performing mechanochemical and photochemical modification of the organic ligand, followed by the assembly with a metal salt. The photoreaction used for this purpose could be, for example, C- H activation.

[00141] The photo-mechanochemical process can also be used to conduct the synthesis of conductive organic polymers, for example poly(diacetylene) and poly(triacetylene) compounds by 1,4-diacetylene polymerization and 1, 6 -tri acetylene polymerization. Other examples of D, D-oligoacetylene polymerizations are also possible.

[00142] The method 800 may be used with a grinding apparatus having a chamber to receive the material to be ground that is fixed to the grinding apparatus, where a radiation source is connected to the grinding apparatus such that the radiation may enter the chamber and irradiate the material to be ground. An exemplary grinding apparatus may be a grinding mill (e.g. ball mill, attrition mill), a twin screw extruder, etc.

[00143] In some embodiments, the material to be ground and the grinding material may be placed in a chamber (e.g. a milling vessel) at step 801. In some examples where the grinding apparatus is a twin screw extruder, the step may not require adding the grinding material, as the twin screws of the extruder may perform the grinding.

[00144] Optionally, the milling vessel may be placed in a radiation vessel (e.g. radiation vessel 500) as described herein at step 802. In such examples, the milling vessel may provide for at least a radiation transparent portion (in some examples, the entire milling vessel may be transparent to the radiation of the radiation source). In other examples, the radiation vessel may also act as the milling vessel, the material to be ground placed in the radiation vessel.

[00145] Optionally, when a radiation vessel is used, the radiation vessel may then be fastened to the grinding apparatus at step 803. For instance, the radiation vessel may be placed in and fastened by a clamp of a ball mill, the clamp securing the radiation vessel in place.

[00146] In other examples, the milling vessel may be fixed directly to the milling apparatus. It will also be understood that in some examples, the milling vessel is integrated to, or part of, the grinding apparatus (such as in the case of some attrition mills). In these examples, the milling vessel may be already fastened to the grinding apparatus.

[00147] The radiation source is then activated at step 804, resulting in the irradiation of the material to be ground. In some examples, the radiation source may be activated by using a user input interface (or a switch) connected to a controller or to circuitry, where the user presses a button to activate the radiation source. In other examples, the radiation source may be activated when a sensor detects the presence of the milling vessel or radiation vessel, the placing of a door or hood in a closed position (e.g. when a hatch of a chamber of the grinding apparatus opens onto the space that receives the material to be ground, a sensor may detect the closing of the hatch, the closing resulting in the activating of the radiation source; e.g. in some examples where the grinding apparatus is a ball mill, there may be a protective hood or shield that covers the milling vessel or radiation vessel prior to the milling; where the lowering of the hood or shield may be detected by the sensor, resulting in the activating of the radiation source), etc.

[00148] The grinding apparatus is activated at step 805, resulting in the grinding of the material to be ground. In some embodiments, when the vessel (milling vessel and/or radiation vessel) contains the grinding material, the activation of the grinding apparatus may result in the oscillation (e.g. shaking, stirring and/or rotating) of the fixed vessel, where the grinding material exerts a mechanical force on the material to be ground. In some examples, such as when the grinding apparatus is a twin screw extruder, the screws perform the grinding of the material to be ground. In some examples, the activation may be triggered by providing the appropriate input on a user input interface, connected to a controller for starting and stopping the apparatus (e.g. pressing the "start" button). In some examples, the activation may be triggered by closing, for example, a hatch providing access to the inner space of the vessel or chamber where the material to be ground is placed, the closing of the hatch, e.g. detected by, e.g., a contact sensor, where the sensor sends a signal that is received and results in the activation of the grinding apparatus.

[00149] It will be understood that steps 804 and 805, respectively involving the radiating and grinding, may be performed simultaneously (e.g. where activating the grinding apparatus may lead to the activation of the radiation source). Moreover, in some examples, the activating of the grinding apparatus may be performed prior to the activating of the radiation source.

[00150] Optionally, the radiation vessel (and/or the milling vessel) may be removed from the grinding apparatus once the irradiation and grinding is complete at step 806. In the examples where the vessel for receiving the material to be ground is integrated to the machine, the barrier or hatch providing access to the chamber may be opened in order to access the irradiated and milled product.

[00151] The irradiated and ground product is then obtained at step 807. In some examples, the irradiated and ground product may be an intermediary product, used, e.g., used to produce a final product or finished product that is to be sold and/or shipped.

[00152] THE GRINDING AND IRRADIATING MILL:

[00153] Reference is now made to Figure 9, illustrating an exemplary grinding mill 900 configured to provide for the simultaneous grinding and irradiating of a material to be ground. The grinding mill 900 is depicted in Figure 9 as an exemplary ball mill for the purposes of an exemplary illustration, but it will be understood that the grinding mill may be another form of grinding mill, such as a chopping mill, attrition mill, etc., without departing from the present teachings.

[00154] The mechanism of the grinding mill that performs the oscillation, shaking, stirring and/or rotating of the vessel fixed thereon, e.g. contained in housing 902, may be one as is known in the art. The grinding mill 900 may include at least one shaft 904 connected to at least one drive 903. The shaft 904 may be directly or indirectly connected to a fastener for securing the milling vessel 205. The shaft 904 may also extend into the vessel, where the shaft may have extrusions that exert a force onto the grinding material and the material to be ground, resulting in the grinding. The shaft 904 performs a repetitive movement such as rotations, or a repetitive motion along one, two or three axes.

[00155] In some examples, there may be more than one fastener 901 for receiving more than one milling vessel 205.

[00156] The grinding mill 900 has a fastener 901 for receiving and securing the milling vessel 205. The fastener 901 may be a clamp as shown in Figure 9, where the clamp may be adjustable to the dimensions of the milling vessel 205. In other examples, the fastener may be a series of bolts to fix the milling vessel to a surface (e.g. such as in the case of an attrition mill), a vice, a receptacle for receiving the milling vessel 205, etc.

[00157] The grinding mill 900 also had a shield 905. The shield 905 may be used to protect users from, e.g. potential projectiles and debris that may dislodge themselves during the grinding (e.g. due to the high speeds of the oscillating movements). The shield 905 may also be a hatch giving access to the inner space of a milling vessel for containing the material to be ground. The shield 905 may also be configured to prevent ambient light from reaching the mill vessel.

[00158] The shield 905 has an open position and a closed position. In the open position, a user may access the inner space of the milling vessel 205, including its contents. In the closed position, the user does not have access to the contents of the milling vessel 205 (and the inner space of the milling vessel 205). In some examples, the shield 905 may be connected to the grinding mill 900 using a connector 906 (e.g. where the connector may pivot around its connection point to the housing 902).

[00159] In some examples, the shield 905 may be used to prevent ambient light from reaching the milling vessel 205 and its contents.

[00160] The grinding mill 900 also has a radiation source 521 fixed thereon. The radiation source 521 is positioned in the grinding mill 900 such that radiation emitted by the radiation source 521 is permitted to enter the milling vessel 205 and irradiate the material to be ground. As a result, the radiation source 521 may be placed in proximity of the milling vessel 205. Examples of positions of a radiation source 521 are depicted in Figure 9. For instance, the radiation source 521 may be present on the fastener 901 (e.g. where the milling vessel may have a radiation transparent portion in proximity of the portion of the fastener 901 providing the radiation source 521). In some examples, the radiation source 521 may be positioned on a front surface of the grinding mill, facing the milling vessel, where the radiation travels to the milling vessel 205. In some examples, the radiation source 521 may be positioned on the shield 905, such that when the shield is placed in a closed position, the radiation source 521 is in proximity of the milling vessel 205 and may transmit radiation to its contents (e.g. via the radiation transparent portion of the milling vessel 205).

[00161] In some examples, at least one surface of the grinding mill 900 (e.g. surfaces of the inside of the shield 905) may be coated in a reflective material configured to reflect the radiation produced by the radiation source 521.

[00162] In some examples, the grinding mill 900 may have at least one sensor 907 for detecting when the shield is in an open position and/or a closed position. The sensor 907 may be, e.g., a proximity sensor or a contact sensor. The sensor 907 may provide a signal that is received by a controller, where the controller may activate the radiation source 521 when the signal indicates that the shield 905 is in its closed position. Similarly, the controller may turn off the radiation source 521 when the sensor provides an indication that the shield 905 is no longer in the closed position (e.g. in the case where the sensor 907 is a two-part contact sensor, when the parts of the contact sensor no longer meet).

[00163] In other embodiments, the activation or deactivation of the radiation source 521 may be controlled manually, where the grinding mill 900 includes a user input interface including, for example, a "start/stop" button. The relative input may result in a signal that, when received by the controller, turns on or off the radiation source. In other examples, the input may turn on /off the radiation source 521 and respectively start/stop the grinding.

[00164] Although the invention has been described with reference to preferred embodiments, it is to be understood that modifications may be resorted to as will be apparent to those skilled in the art. Such modifications and variations are to be considered within the purview and scope of the present invention.

[00165] Representative, non-limiting examples of the present invention were described above in detail with reference to the attached drawing. This detailed description is merely intended to teach a person of skill in the art further details for practicing preferred aspects of the present teachings and is not intended to limit the scope of the invention. Furthermore, each of the additional features and teachings disclosed above and below may be utilized separately or in conjunction with other features and teachings.

[00166] Moreover, combinations of features and steps disclosed in the above detailed description, as well as in the experimental examples, may not be necessary to practice the invention in the broadest sense, and are instead taught merely to particularly describe representative examples of the invention. Furthermore, various features of the above-described representative examples, as well as the various independent and dependent claims below, may be combined in ways that are not specifically and explicitly enumerated in order to provide additional useful embodiments of the present teachings.

Claims

What is claimed is:

1. A radiation vessel for use in a milling system comprising a grinding mill, a radiation source and a milling vessel comprising grinding material and a material to be ground, comprising:

a first end;

a second end diametrically opposite to said first end;

an opening shaped to receive a milling vessel;

a hollow elongated body spanning a length defined by said first end and said second end, wherein said elongated body defines a space for receiving said milling vessel, wherein said opening allows for the insertion of said milling vessel into said space through said opening; and a radiation compartment shaped to receive a radiation source for producing radiation, wherein said radiation compartment comprises a radiation opening configured and positioned with respect to said space to allow transmission of said radiation from said radiation source to said space,

wherein said radiation vessel is shaped to be fitted to said grinding mill.

2. The radiation vessel as defined in claim 1, wherein said hollow elongated body is of a cylindrical shape.

3. The radiation vessel as defined in claim 1 or claim 2, wherein said opening is present on said second end, and said opening has an elliptical shape.

4. The radiation vessel as defined in claim 3, wherein said opening is of a circular shape.

5. The radiation vessel as defined in claim 3 or claim 4, further comprising a top shaped to seal said opening of said second end.

6. The radiation vessel as defined in claim 5, wherein said radiation compartment is located in said top, such that said radiation source transmits radiation to said space when said top is fitted to said opening and said radiation source is received within said radiation compartment.

7. The radiation vessel as defined in any one of claims 1 to 5, wherein said radiation compartment is connected to or integrated to said elongated body.

8. The radiation vessel as defined in any one of claims 1 to 7, further comprising said radiation source.

9. The radiation vessel as defined in claim 8, wherein said radiation source is a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

10. The radiation vessel as defined in any one of claims 1 to 9, further comprising one of: a connector for connecting to a power source and providing power to said radiation source from said power source; and

a power source.

1 1. The radiation vessel as defined in any one of claims 1 to 10, further comprising a heat sink positioned to evacuate heat produced by at least said radiation source.

12. A method of producing a product comprising:

providing a grinding apparatus fixed to a chamber comprising an inner space that has received a material to be ground; and

grinding said material to be ground while irradiating said material to be ground using a radiation source, wherein said radiation source is connected to said grinding apparatus such that radiation may travel into said inner space.

13. The method as defined in claim 12, wherein said grinding apparatus is a grinding mill, and wherein said grinding is performed by grinding material contained in said chamber, said grinding material applying a mechanical force to said material to be ground as said chamber is at least one of shaken, stirred and rotated by said grinding mill.

14. The method as defined in claim 13, wherein said chamber that is provided comprises a radiation transparent portion configured to permit radiation from outside said inner space to enter said inner space.

15. The method as defined in any one of claims 12 to 14, wherein said radiation source is fixed to said chamber.

16. The method as defined in any one of claims 12 to 15, wherein said grinding apparatus is a twin screw extruder, and wherein said grinding is performed by the screws of said twin screw extruder.

17. The method as defined in any one of claims 12 to 16, wherein radiation is used to disinfect the contents of said vessel.

18. The method as defined in any one of claims 12 to 17, wherein said irradiating is used for a chemical reaction involving said material to be ground as a reagent.

19. The method as defined in any one of claims 12 to 18, wherein said radiation source is a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

20. The method as defined in any one of claims 12 to 19, wherein said chamber is integrated to said grinding apparatus.

21. The method as defined in any one of claims 12 to 20, wherein said chamber is a vessel that is fixed to said grinding apparatus via a fastener.

22. The method as defined in any one of claims 12 to 21, further comprising dissipating heat resulting from said radiation source via a heat sink.

23. A method of producing a final product comprising:

producing an intermediary product by performing the method as defined in any one of claims 12 to 22; and

at least one of transforming and combining said intermediary product to produce said final product.

24. A grinding mill for grinding and irradiating a target material comprising:

a fastener for retaining a milling vessel;

a drive for causing at least one of shaking, stirring and rotating of said vessel received in said fastener;

a radiation compartment configured to receive a radiation source, wherein said radiation compartment is configured to position said received radiation source so as to allow for the irradiation of said milling vessel by said radiation source when said milling vessel is retained by said fastener; and

a shield adapted to change from an open position to a closed position,

wherein, in said open position, said shield allows access to said fastener, and

in said closed position, said shield covers said milling vessel retained by said fastener, and said shield covers in said closed position said radiation source.

25. The grinding mill as defined in claim 24, further comprising said radiation source.

26. The grinding mill as defined in claim 25, wherein said radiation source is a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

27. The grinding mill as defined in any one of claims 24 to 26, wherein said radiation compartment is present in said fastener.

28. The grinding mill as defined in any one of claims 24 to 27, wherein said radiation compartment is present in said shield.

29. The grinding mill as defined in any one of claims 24 to 28, further comprising circuitry configured to cause said radiation source to produce radiation when said shield is in a closed position.

30. The grinding mill as defined in any one of claims 24 to 29, further comprising circuitry configured to cause said radiation source to cease producing radiation when said shield changes from said closed position to said open position.

31. The grinding mill as defined in any one of claims 24 to 30, wherein said shield is one of a retractable hood and a hatch.

32. The grinding mill as defined in any one of claims 24 to 31, wherein said fastener is a clamp that is adjustable to accommodate to the width of said milling vessel.

33. An apparatus used for simultaneously milling and irradiating a material to be ground comprising:

a milling vessel configured to receive a material to be ground and a grinding material, said milling vessel comprising at least a radiation transparent portion; and

a radiation vessel comprising a radiation compartment shaped to receive a radiation source, wherein said radiation compartment is configured to position said received radiation source such that radiation produced by said radiation source irradiates said material to be ground via said at least a radiation transparent portion of said milling vessel.

34. The apparatus as defined in claim 33, wherein said milling vessel and said radiation vessel are integrated, forming a single vessel with an inner space for receiving said material to be ground and said grinding material.

35. The apparatus as defined in claim 33 or claim 34, further comprising a top configured to seal said opening of said radiation vessel.

36. The apparatus as defined in any one of claims 33 to 35, further comprising said radiation source.

37. The apparatus as defined in claim 36, wherein said radiation source is a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

38. The apparatus as defined in any one of claims 33 to 38, further comprising a grinding mill configured to receive at least said radiation vessel, and to at least one of shake, stir and rotate said radiation vessel, causing said material to be ground and said grinding media to be at least one of shaken, stirred and rotated.

39. The apparatus as defined in claim 38, wherein said grinding mill is a ball mill.

40. The apparatus as defined in any one of claims 33 to 39, wherein said milling vessel is of a cylindrical shape.

41. The apparatus as defined in claim 40, wherein at least one base of said milling vessel is hemispherical.

42. The apparatus as defined in claim 33 to 41, wherein said at least a radiation transparent portion is the entire milling vessel.

43. The apparatus as defined in any one of claims 33 to 42, wherein said at least a radiation transparent portion is composed of at least one of poly(methyl methacrylate), polycarbonate, fiber glass, sapphire, quartz, and glass.

44. The apparatus as defined in any one of claims 33 to 43, wherein said milling vessel comprises precious metal catalysts deposited on its interior surface.

45. The apparatus as defined in claim 44, wherein said precious metal catalysts deposited on the interior surface of the milling vessel includes at least one of ruthenium, rhodium, palladium, silver, gold, platinum, iridium, and mixtures thereof.

46. The apparatus as defined in any one of claims 33 to 45, further comprising a heat sink to dissipate heat produced by at least said radiation source.

47. The apparatus as defined in any one of claims 33 to 46, further comprising a power source.

48. The apparatus as defined in claim 47, wherein said power source is a battery.

49. The apparatus as defined in any one of claims 33 to 48, further comprising a connector to connect to a power outlet.

50. The apparatus as defined in any one of claims 33 to 49, further comprising a wireless power receiver to receive power wirelessly from a source of wireless power.

51. The apparatus as defined in any one of claims 33 to 50, further comprising said grinding media, wherein said grinding media includes at least one of metal, rubber, ceramic, plastic, Teflon, glass balls, flint pebbles, and tungsten carbide.

52. The apparatus as defined in any one of claims 33 to 51, wherein said milling vessel comprises an alloyed metal.

53. The apparatus as defined in claim 52, wherein said alloyed metal includes at least one of stainless steel, carbon steel, brass, bronze, and mixtures thereof.

54. The apparatus as defined in any one of claims 33 to 53, wherein said milling vessel comprises a base metal.

55. The apparatus as defined in claim 54, wherein said base metal comprises copper, nickel, gold, silver, and mixtures thereof.

56. A simultaneous irradiation and milling system comprising: a milling chamber for containing grinding media and a material to be ground, the milling chamber including a radiation transparent portion;

a radiation chamber into which the milling chamber is placed;

a mill that shakes, stirs or rotates the milling chamber and grinds the material to be ground with the grinding media by a shaking, stirring or rotation action; and

a radiation source optically coupled to the radiation chamber that simultaneously transmits radiation that passes through the radiation transparent portion of the milling chamber and interacts with the material to be ground as the mill rotates the milling chamber and grinds the material.

57. A simultaneous irradiation and milling system as defined in claim 56, further comprising:

a power source that supplies energy to the radiation source.

58. A simultaneous irradiation and milling system as defined in claim 56 or claim 57, wherein the milling chamber and the radiation chamber are an integrated combined chamber.

59. A simultaneous irradiation and milling system as defined in any one of claims 56 to 58, further comprising a lid that seals the milling chamber.

60. A simultaneous irradiation and milling system as defined in claim 59, wherein the lid includes a radiation port through which radiation enters the milling chamber.

61. A simultaneous irradiation and milling system as defined in any one of claims 56 to 60, further comprising a grinding media inlet for feeding grinding media into the milling chamber.

62. A simultaneous irradiation and milling system as defined in any one of claims 56 to 61, further comprising a material to be ground inlet for introducing material to be ground into the milling chamber.

63. A simultaneous irradiation and milling system as defined in any one of claims 56 to 62, further comprising a ground material outlet for discharging material to be ground that has ground or dispersed from the milling chamber.

64. A simultaneous irradiation and milling system as defined in any one of claims 56 to 63, wherein the grinding media includes at least one of metal, rubber, ceramic, plastic, Teflon, glass balls, flint pebbles, and tungsten carbide.

65. A simultaneous irradiation and milling system as defined in any one of claims 56 to 64, wherein the radiation source is a source of at least one of ultraviolet radiation, visible light, infrared, X-ray, and gamma radiation.

66. A simultaneous irradiation and milling system as defined in any one of claims 56 to 65, wherein the radiation transparent portion of the milling chamber includes at least one of poly(methyl methacrylate), polycarbonate, fiber glass, sapphire, quartz, and glass.

67. A simultaneous irradiation and milling system as defined in any one of claims 56 to 66, wherein the milling chamber comprises an alloyed metal.

68. A simultaneous irradiation and milling system as defined in claim 67, wherein the alloyed metal includes at least one of stainless steel, carbon steel, brass, bronze, and mixtures thereof.

69. A simultaneous irradiation and milling system as defined in any one of claims 56 to 68, wherein the milling chamber comprises a base metal.

70. A simultaneous irradiation and milling system as defined in claim 69, wherein the base metal includes copper, nickel, gold, silver, and mixtures thereof.

71. A simultaneous irradiation and milling system as defined in any one of claims 56 to 70, wherein the milling chamber comprises a plastic.

72. A simultaneous irradiation and milling system as defined in claim 71, wherein the plastic includes at least one of polycarbonate, polyetherether ketone, poly (methyl methacrylate), Teflon, and mixtures thereof.

73. A simultaneous irradiation and milling system as defined in any one of claims 56 to 72, wherein the milling chamber comprises at least one of an inorganic compound and a composite material.

74. A simultaneous irradiation and milling system as defined in any one of claims 56 to 73, wherein the milling chamber comprises tungsten carbide.

75. A simultaneous irradiation and milling system as defined in any one of claims 56 to 74, wherein the milling chamber includes precious metal catalysts deposited on its interior surface.

76. A simultaneous irradiation and milling system as defined in claim 75, wherein the precious metal catalysts deposited on the interior surface of the milling chamber includes at least one of ruthenium, rhodium, palladium, silver, gold, platinum, iridium, and mixtures thereof.