US20190055171A1 - Energetic materials - Google Patents

Energetic materials Download PDF

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Publication number
US20190055171A1
US20190055171A1 US16/087,440 US201716087440A US2019055171A1 US 20190055171 A1 US20190055171 A1 US 20190055171A1 US 201716087440 A US201716087440 A US 201716087440A US 2019055171 A1 US2019055171 A1 US 2019055171A1
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Prior art keywords
composition
energetic
radiation curable
meth
acrylate
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Inventor
Michiel Hannes STRAATHOF
Christoffel Adrianus Van Driel
Aafke Tessa Ten Cate
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Assigned to NEDERLANDSE ORGANISATIE VOOR TOEGEPAST- NATUURWETENSCHAPPELIJK ONDERZOEK TNO reassignment NEDERLANDSE ORGANISATIE VOOR TOEGEPAST- NATUURWETENSCHAPPELIJK ONDERZOEK TNO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TEN CATE, AAFKE TESSA, VAN DRIEL, CHRISTOFFEL ADRIANUS, Straathof, Michiel Hannes
Publication of US20190055171A1 publication Critical patent/US20190055171A1/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0058—Shaping the mixture by casting a curable composition, e.g. of the plastisol type
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product

Definitions

  • the invention is directed to a radiation curable energetic composition, to a method of forming a three-dimensional energetic object, to a three-dimensional energetic object, and to uses of the radiation curable energetic composition.
  • Propellant charges are used in pyrotechnics and ballistics in order to accelerate a piston or a projectile.
  • the propellant charge is ignited by a primer, which is a small amount of sensitive explosive. Gases produced by combustion of the propellant charge cause a rapid build-up of pressure. When a certain pressure is reached, the projectile begins to move, thereby causing an increase in chamber volume. After a pressure maximum is reached, typically the pressure decreases relatively rapidly due to the expansion of the chamber volume.
  • a propellant charge is an amount of relatively insensitive but powerful energetic material that propels the projectile out of the gun barrel.
  • Various types of propellant charges having different composition and geometries are used for different applications and purposes.
  • the propellants used are typically solid. Examples of propellants that are in use today include gun powders, including smokeless powders. Smokeless powders may be considered to be classed as either single or multi-base powders. Conventional smokeless powders consist mainly of nitrocellulose. Typical production processes include drying of water-wet nitrocellulose, mixing and kneading with ether and alcohol and other constituents, pressing the propellant dough through a die, cutting the obtained strand into propellant grains, and drying these grains. Although called powders, they are not in powder form, but in granule form.
  • nitrocellulose is the main energetic material present.
  • Other ingredients and additives are added to obtain suitable form, desired burning characteristics, and stability.
  • the multi-base propellants may be divided into double-base and triple-base propellants, both of which contain typically nitroglycerin to facilitate the dissolving of the nitrocellulose and enhance its energetic qualities.
  • the nitroglycerin also increases the sensitivity, the flame temperature, burn rate, and tendency to detonate. The higher flame temperature serves to decrease the smoke and residue, but increases flash and gun-tube erosion.
  • Triple-base propellants are double-base propellants with the addition of nitroguanidine to lower the flame temperature, which produces less tube erosion and flash.
  • the major drawback is the limited supply of the raw material nitroguanidine.
  • the multiple ingredients are evenly distributed in the propellant charge.
  • the projectile is either at rest or moving relatively slowly.
  • gases are being generated faster than the volume of the chamber is increasing.
  • the pressure experienced increases.
  • the volume of the chamber increases at a rate which ultimately surpasses the rate of gas generation by the burning of the propellant material.
  • the transition corresponds to the point of maximum pressure in the combustion chamber.
  • the pressure decreases as the projectile continues to accelerate thus increasing the volume of the chamber at a rate faster than the increase in volume of gases being generated by the propellant burn.
  • Solid propellants are designed to produce a large volume of gases at a controlled rate.
  • Gun barrels and some rocket casings are designed to withstand a fixed maximum gas pressure.
  • the pressure generated can be limited to this maximum value by controlling the rate of burning of the propellant.
  • the burn rate is controlled by varying the following factors:
  • 4,386,569 accordingly describes a propellant grain of generally cylindrical shape having a plurality of longitudinal substantially parallel perforations extending there through, the cross-sectional locations of said perforations being such that the interstitial distances between adjacent perforations is substantially equal and substantially equals the extrastitial distances between the perimetric perforations and the outer surface of the grain wall.
  • Curable energetic compositions have been explored in the art as well.
  • U.S. Pat. No. 4,050,968 and U.S. Pat. No. 4,283,237 describe a curable explosive composition that may be cured using heat.
  • curing energetic compositions by heat may lead to undesirable safety issues because of proximity to the decomposition temperature of energetic materials that are present.
  • heat curing can lead to bad resolution in additive manufacturing processing, and in general yields a process that is difficult to control.
  • Object of the present invention is to overcome one or more of the disadvantages of the prior art.
  • the invention is directed to a radiation curable energetic composition, comprising
  • an energetic component as used in this application is meant to refer to any substance or mixture of substances that, through chemical reaction, is capable of rapidly releasing energy.
  • an energetic component comprises fuel and oxidiser.
  • energetic materials are solid, liquid or gaseous substances or mixtures which are capable of very fast chemical reactions without the use of additional reactive species (e.g. oxygen).
  • the reaction can be initiated by means of mechanical, thermal or shock wave stimuli.
  • the reaction products are gaseous.
  • Energetic components can be applied in explosives, rocket and gun propellants, pyrotechnics, gas generators etc.
  • the energetic components of the present invention are distinguished from solid propellants used in hybrid rockets, which are only capable of a chemical reaction once they are brought into contact with the additional liquid (or gas) propellant that is initially kept separate from the solid propellant.
  • Such propellants for hybrid rockets are, for instance, known from US-A-2009/0 217 525 and US-A-2013/0 042 596.
  • energetic composition as used in this application is meant to refer to a composition that comprises one or more energetic components.
  • burn rate as used in this application is meant to refer to the rate at which a propellant charge releases gas during combustion.
  • the burn rate is commonly measured as the mass of pyrotechnic composition consumed per unit time, e.g., g/s.
  • the term “linear burn rate” as used in this application is meant to refer to the distance the burning surface of a pyrotechnic composition advances inwardly (perpendicular to the burning surface) per unit time.
  • the linear burn rate is commonly reported as distance per unit time, e.g., mm/s.
  • additive manufacturing as used in this application is meant to refer to a method of making a three-dimensional solid object from a digital model. Additive manufacturing is achieved using an additive process, where successive layers of material are laid down in different shapes. Additive manufacturing is sometimes known as “3D printing”, “additive layer manufacturing” (ALM) or “rapid prototyping”. More in particular, additive manufacturing is a group of processes characterised by manufacturing three-dimensional components by building up substantially two-dimensional layers (or slices) on a layer by layer basis.
  • Each layer is generally very thin (for example between 20-1000 ⁇ m, 20-800 ⁇ m, 20-500 ⁇ m, or even 20-100 ⁇ m) and many layers are formed in a sequence with the two-dimensional shape varying on each layer to provide the desired final three-dimensional profile.
  • additive manufacturing processes progressively add material to form a net shape or near net shape final component.
  • the invention allows to better regulate the burning of the propellant charge or grain so as to prolong the period of maximum pressure at which the projectile is accelerated. As a result of the prolonged period of maximum pressure, the projectile will be given a higher speed.
  • the production of energetic objects by means of additive manufacturing allows to provide the end product with specific properties that were heretofore not possible.
  • the composition may also be extruded, followed by curing. This provides further degrees of freedom for manufacturing new end products.
  • the energetic composition of the invention is curable by means of radiation, more particular electromagnetic radiation.
  • the electromagnetic radiation can be selected from the group consisting of X-rays, ultraviolet light, visible light, infrared radiation and combinations thereof.
  • the one or more polymerisable components comprise one or more energetic polymerisable components.
  • the radiation curable energetic composition of the invention can comprise a free radical polymerisation system consisting of (a1) one or more free radical polymerisable components and (b1) one or more polymerisation photoinitiators for free radical polymerisation.
  • the radiation curable composition of the invention can comprise a cationic polymerisation system consisting of (a2) one or more cationically polymerisable components and (b2) one or more polymerisation photoinitiators for cationic polymerisation.
  • the amount of polymerisable components in the composition can suitably be 5-45% by total weight of the composition, preferably 10-40%, more preferably 15-35%.
  • These polymerisable components can include free radical polymerisable components and cationically polymerisable components.
  • the polymerisable component at least comprises a free radical polymerisable component.
  • Suitable free radical polymerisable components include aliphatic (meth) acrylates, aromatic (meth)acrylates, cycloaliphatic (meth) acrylates, arylaliphatic (meth)acrylates, and heterocyclic (meth)acrylates, (cyclo)aliphatic vinyl ethers, aromatic vinyl ethers, (cyclo)aliphatic allyl ethers, unsaturated polyesters, alkenes, styrene, or combinations thereof.
  • the free radical polymerisable components may comprise monomers, oligomers, and/or polymers. They may be monofunctional or polyfunctional, i.e. have one or more functional groups that can polymerise by free radical polymerisation.
  • Examples of monofunctional free-radical polymerisable components include isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylatea, 4-butylcyclohexyl (meth) acrylate, acryloyl morpholine (meth)acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth)acrylate, butyl (meth) acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate,
  • polyfunctional free radical polymerisable components include those with (meth)acryloyl groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol diacrylate, bisphenol A diglycidyl ether di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, [2-[1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methyl acrylate, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane di(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, proposylated trimethylolpropan
  • the one or more polymerisable components in the radiation curable energetic composition of the invention comprises one or more energetic free radical polymerisable components.
  • Suitable examples of energetic free radical polymerisable components include 2,2,2-trinitroethyl (meth) acrylate, 2,2-dinitropropyl (meth) acrylate, 2,2-dinitropropyl di(meth)acrylate, 2-nitroethyl (meth) acrylate, beta-nitratoethyl (meth)acrylate, and pentaerythritol trinitrate (meth)acrylate.
  • energetic free radical polymerisable components include fluoroacrylates, such as 1,1,7-trihydroperfluoroheptyl(meth)acrylate, 1,1-dihydroperfluorooctyl(meth)acrylate, 1,2,4,5-tetrakis(difluoroamino)amyl (meth) acrylate, 2,3-bis(difluoroaminopropyl) (meth) acrylate, 2-(N-butyl)-perfluorooctane sulphonamide ethylacrylate, 2,-fluoro-2,2-dinitroethylacrylate. Any combination of the above mentioned free radical polymerisable components may be used.
  • the free radical polymerisable component may be present in the composition in an amount of 5-45% by total weight of the composition, preferably 10-40%, more preferably 15-35%.
  • a free radical polymerisable component is used together with a polymerisation photoinitiator for free radical polymerisation.
  • a polymerisation photoinitiator for free radical polymerisation can be classified in photoinitiators that form radicals by cleavage, known as “Norrish type I”, and photoinitiators that form radicals by hydrogen abstraction, known as “Norrish type II”.
  • the Norrish type II photoinitiators require a hydrogen donor, which serves as the free radical source.
  • Photolysis of aromatic ketones such as benzophenone, thioxanthones, benzyl, and quinones
  • hydrogen donors such as alcohols, amines, or thiols
  • the photopolymerisation of vinyl monomers is usually initiated by the radicals produced from the hydrogen donor.
  • the ketyl radicals are usually not reactive toward vinyl monomers because of the steric hindrance and the delocalisation of an unpaired electron.
  • photoinitiators for free radical polymerisation examples include 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop anone-1, 2-benzyl-2-(dimethylamino)-1[4-(4-moprholinyl)phenyl]-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-benzyl)-butan-1-one, 4-benzoyl-4′-methyl diphenyl sulphide, 4,4′-bis(diethylamino)benzophenone, and 4,4′-bis(N,N′-dimethylamino)benzophenone (Michler'
  • Preferred photoinitiators for free radical polymerisation include 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.
  • the polymerisation photoinitiator for free radical polymerisation may be present in the composition in an amount of 0.05-3% by total weight of the composition, such as 0.1-2%, or 0.2-1.5%.
  • cationically polymerisable components include cyclic ether compounds such as epoxy compounds and oxetanes, cyclic lactone compounds cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds and vinyl ether compounds.
  • cationically polymerisable components include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglydicyl ether, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexne-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane,
  • the cationically polymerisable component may be present in the composition in an amount of 5-45% by total weight of the composition, preferably 10-40%, more preferably 15-35%. If the cationically polymerisable component comprises an oxetane, then the oxetane is usually present in an amount of 5-20% by total weight of the composition, such as 7-15%.
  • a cationically polymerisable component is used together with a polymerisation photoinitiator for cationic polymerisation.
  • Suitable photoinitiators for cationic polymerisation include onium salts, halonium salts, iodosyl salts, selenium salts, sulphonium salts, sulphoxonium salts, diazonium salts, metallocene salts, isoquinolinium salts, phosphonium salts, arsonium salts, tropylium salts, dialkylphenacylsulphonium salts, thiopyrilium salts, diaryl iodonium salts, triaryl sulphonium salts, ferrocenes, di(cyclopentadienyliron)arene salt compounds, pyridinium salts, and combinations thereof.
  • the photoinitiator for cationic polymerisation can be selected from triarylsulphonium salts, diaryliodonium salt
  • the photoinitiator for cationic polymerisation can suitably have an anion selected from the group consisting of BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , PF 6 ⁇ , [B(CF 3 ) 4 ] ⁇ , B(C 6 F 5 ) 4 ⁇ , B[C 6 H 3 -3,5(CF 3 ) 2 ] 4 ⁇ , B(C 6 H 4 CF 3 ) 4 ⁇ , B(C 6 H 3 F2) 4 ⁇ , B[C 6 F 4 -4(CF 3 )] 4 ⁇ , Ga(C 6 F 5 ) 4 ⁇ , [(C 6 F 5 ) 3 B—C 3 H 3 N 2 —B(C 6 F 5 ) 3 ] ⁇ , [(C 6 F 5 ) 3 —NH 2 —B(C 6 F 5 ) 3 ] ⁇ , tetrakis(3,5-difluoro-4-alkyloxypheny
  • photoinitiators for cationic polymerisation include 4-[4-(3-chlorobenzoyl)phenylthio]phenyl bis(4-fluorophenyl)sulphonium hexafluoroantimonate, 4-[4-(3-chlorobenzoyl)phenylthio]phenyl bis(4-fluorophenyl)sulphonium tetrakis(pentafluorophenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenyl bis(4-fluorophenyl)sulphonium tetrakis(3,5-difluoro-4-methyloxyphenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenyl bis(4-fluorophenyl)sulphonium tetrakis(2,3,5,6-tetrafluoro-4-methyloxyphenyl
  • aromatic triaryl sulphonium salts as photoinitiator for cationic polymerisation is desirable in additive manufacturing because the resulting composition attains a fast photospeed, good thermal stability, and good photo stability.
  • the polymerisation photoinitiator for cationic polymerisation may be present in the composition in an amount of 0.05-3% by total weight of the composition, such as 0.1-2%, or 0.2-1.5%.
  • the energetic component that is comprised in the radiation curable energetic composition of the invention may be polymerisable or non-polymerisable.
  • at least part of the energetic components in the energetic composition are polymerisable components.
  • components (a) and (c) may overlap.
  • at least part (such as all) of the energetic components are radiation curable components, i.e. can be cured by exposing the components to actinic radiation.
  • Suitable energetic materials include 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythrol tetranitrate (PETN), 3-nitro-1,2,4-triazol-5-one (NTO), nitroglycerine (NG), nitrocellulose (13% N) (NC), ammonium nitrate (AN), potassium nitrate, hydrazine nitrate, lithium nitrate, ammonium perchlorate (AP), potassium perchlorate, 2,4,6,8,10,12-(hexanitro-hexaaza)tetracyclododecane (CL20 or HNIW), 1,3,3-trinitroazetidine (TNAZ), octanitrocubane (ONC), 1,1-diamino-2,2-dinitroethene (FOX-7), ammonium
  • the energetic component can be liquid or solid. Preferably, at least part of the energetic component is solid. In an embodiment the energetic component is solid.
  • the solid energetic component can be in the form of particulates, which may have an average particle size as determined by laser diffraction of 0.5-100 ⁇ m, preferably 1-60 ⁇ m, more preferably 2-40 ⁇ m. Such particles have excellent burn behaviour and mechanical strength, Smaller particles are not preferred due to the increase in viscosity.
  • the solid energetic component can also be in the form of nanoparticles.
  • the energetic component may be present in the composition in an amount of 30% or more by total weight of the composition, such as 40-95%, or 45-90%. These amounts include the possibility that polymerisable components and optional plasticiser in the composition are also energetic components.
  • the radiation curable energetic composition of the invention may further comprise a hydroxy functional component.
  • the hydroxy functional component may have a hydroxyl functionality of at least one. Suitable hydroxy functional components preferably contain one or more primary or secondary aliphatic hydroxyl. The hydroxyl group may be internal in the molecule or terminal.
  • Suitable hydroxy functional components include alkanols, monoalkyl ethers of polyoxyalkylene glycols, monoalkyl ethers of alkylene glycols, alkylene and arylalkylene glycols and polyols.
  • suitable hydroxy functional components include 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,3-heptanetriol, 2,6-dimethyl-1,2,6-hexanetriol, (2R,3R)-( ⁇ )-2-benzyloxy-1,3,4-butanetriol, 1,2,3-hexanetriol, 1,2,3-butanetriol, 3-methyl-1,3,5-pentanetriol, 1,2,3-cyclohexanetriol, 1,3,5-cyclohexanetriol, 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, 2-hydroxymethyltetrahydropyran-3,4,5-triol, 2,2,4,4-tetramethyl-1,3-cyclobutanetriol, 1,3-cyclopentanediol, trans-1,2-cyclooctanediol, 1,16-hexadecanediol, 3,6-dithia-1,8-oct
  • oligomeric and polymeric hydroxy functional components can be used.
  • examples thereof include polyoxyethylene and polyoxypropylene glycols and triols with number average molecular weights of 200-10 000 g/mol, polytetramethylene glycols of varying molecular weights, poly(oxyethylene-oxybutylene) random or block copolymers, copolymers containing pendant hydroxy groups formed by hydrolysis or partial hydrolysis of vinyl acetate copolymers, polyvinylacetal resins containing pendant hydroxyl groups, hydroxy-terminated polyesters and hydroxy-terminated polylactones, hydroxy-functionalised polyalkadienes, such as polybutadiene, aliphatic polycarbonate polyols, such as an aliphatic polycarbonate diol, and hydroxy-terminated polyethers, and combinations thereof.
  • Preferred polyether polyols are polypropylene glycols of various molecular weight. Especially preferred are linear and branched polytetrahydrofuran polyether polyols available in various molecular weights, such as in the range of 150-4000 g/mol, in the range of 150-1500 g/mol, or in the range of 150-750 g/mol.
  • the hydroxy functional component may be present in the composition in an amount of 0-10% by total weight of the composition, such as 0-5%, or 0.1-3%, or 0.2-2%.
  • a representative radiation curable energetic composition according to the invention comprises
  • composition of polymerisable components preferably 10-40%, even more preferably 15-35%;
  • composition of polymerisation photoinitiators preferably photoinitiators
  • preferably photoinitiators preferably 0.1-2%, even more preferably 0.2-1.5%
  • composition of energetic components such as 40-95%, or 45-90%
  • hydroxy functional component 0-10% by total weight of the hydroxy functional component, preferably 0.5-8%, even more preferably 1-5%.
  • the radiation curable energetic composition of the invention comprises one or more plasticisers.
  • a plasticiser in the radiation curable energetic composition of the invention is to tune the mechanical properties of the cured object and/or to tune the total energetic value of the composition.
  • the plasticiser may also be added in order to tune the viscosity of the radiation curable energetic composition during additive manufacturing. These plasticisers may or may not be energetic.
  • the one or more plasticisers comprise one or more energetic plasticisers.
  • suitable non-energetic plasticisers include acid esters such as dialkyl esters of phthalic acids, triorgano esters of phosphoric acid, dialkyl esters of adipic acid, trimellitic esters, fatty acid esters, acetic esters, maleic esters, fumaric esters, citric esters.
  • acid esters such as dialkyl esters of phthalic acids, triorgano esters of phosphoric acid, dialkyl esters of adipic acid, trimellitic esters, fatty acid esters, acetic esters, maleic esters, fumaric esters, citric esters.
  • Explicit examples include di-n-octyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate and di-2-ethylhexyl phthalate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate and tricresyl phosphate, dibutyl adipate and di-n-octyl adipate, tri-2-ethylhexyltrimellitate, dimethyl adipate, dibutyl adipate, diisobutyl adipate, diisonorbornyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, diethylene glycol adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dimethyl sebacate
  • suitable energetic plasticisers include alkyl ethyl nitramines, in particular the homologous series based on N-(2-nitroxyethyl) nitramine, NO 2 —N—CH 2 CH 2 ONO 2 .
  • Explicit examples include N-(2-nitroxyethyl) methylnitramine, N-(2-nitroxyethyl) ethylnitramine, N-(2-nitroxyethyl) n-propylnitramine, N-(2-nitroxyethyl) n-butylnitramine, N-(2-nitroxypropyl) methylnitramine and N-(2-nitroxyethyl) cyclohexylnitramine.
  • Further examples include dinitroxydiethyl nitramine, nitroglycerin, 1,2,4-butane triol trinitrate, 1,5-diazido-3-nitrazapentane, bis(2-fluoro-2,2-dinitroethyl)formal, triethyleneglycol dinitrate, bis(2,2-dinitropropyl)formal, bis(2,2-dinitropropyl)acetal, diglycol dinitrate, and combinations thereof.
  • the plasticiser may be present in the composition in an amount of 0-40% by total weight of the composition, such as 10-35%, or 15-30%.
  • the radiation curable energetic composition of the invention comprises a dye and/or a pigment.
  • the dye and/or pigment can, for instance, ensure that the irradiation light is absorbed in the layer that is intended to cure (typically the layer closest to the irradiation source) and that the light does not penetrate deeper to other layers.
  • the amount of dyes and/or pigments in the radiation curable energetic composition can, for instance, be 0-0.1% by total weight of the composition, such as 0.005-0.02% by total weight of the composition.
  • the radiation curable energetic composition of the invention may further comprise one or more additives, such as fuels, oxidisers, dispersants, photosensitisers, fillers, stabilising agents, dyes, pigments, antioxidants, wetting agents, explosive desensitisers, defoamers, and surfactants.
  • the invention is directed to a method of forming a three-dimensional energetic object comprising the steps of forming and selectively curing a layer of the radiation curable energetic composition according to the invention with actinic radiation and repeating the steps of forming and selectively curing a layer of the radiation curable energetic composition according to the invention a plurality of times to obtain a three dimensional energetic object.
  • the obtained three-dimensional energetic object may be subjected to post-curing by heat and/or actinic irradiation.
  • Post-curing can aid in curing possible unreacted components in the radiation curable composition, can control stickiness of the surface of the object, and can improve the initial strength of the object.
  • the actinic radiation used in the method of the invention and in the optional post-curing is preferably ultraviolet radiation.
  • ultraviolet radiation includes typical wavelengths for ultraviolet curing in the range of 200-500 nm (near ultraviolet”).
  • the invention is directed to a three-dimensional energetic object formed from the radiation curable energetic composition or by the method according to the invention.
  • the invention is directed to the use of a radiation curable energetic composition according to the invention in ballistics, pyromechnical devices (including actuators), fireworks or solid or hybrid propellant rockets.
  • a radiation curable energetic composition was prepared by blending the ingredients as mentioned in table 1 in the indicated amounts.
  • Non-energetic binder 24 Energetic plasticiser 1) 24 Dispersant 2) 2 Solid energetic material 3) 50 1) N-(2-nitroxyethyl) ethylnitramine 2) Disperbyk 116 dispersant obtained from Byk 3) RDX (cyclo-1,3,5-trimethylene-2,4,6-trinitramine)
  • the non-energetic binder was composed as indicated in Table 2.

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EP16161647.9 2016-03-22
EP16161647.9A EP3222408A1 (fr) 2016-03-22 2016-03-22 Matières énergétiques
PCT/NL2017/050174 WO2017164731A1 (fr) 2016-03-22 2017-03-22 Matériaux énergétiques

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IT201900005788A1 (it) * 2019-04-15 2020-10-15 Torino Politecnico Processo di produzione di propellente composito tramite deposizione e polimerizzazione foto-attivata per endoreattori a propellente solidi
US11318669B2 (en) * 2016-01-29 2022-05-03 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing
CN115806456A (zh) * 2022-11-23 2023-03-17 西安近代化学研究所 一种添加Co-MOF的光固化火药及其制备方法
WO2024077952A1 (fr) * 2022-10-10 2024-04-18 西安近代化学研究所 Polymère photodurcissable et combustible et son utilisation

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EP3705465A1 (fr) * 2019-03-08 2020-09-09 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO L'impression améliorée d'un matérieau energetique
FR3096047B1 (fr) 2019-05-13 2022-06-24 Eurenco France Grains de poudre propulsive comprenant des canaux au moins partiellement obtures
CN110937962A (zh) * 2019-12-03 2020-03-31 北京理工大学 一种合金型洋红色冷烟花药剂及其制备方法
CN111533629A (zh) * 2020-05-27 2020-08-14 湖南坤普科技有限公司 一种含有硝化纤维的烟花爆竹以及提高其燃速的方法
FR3117399B1 (fr) 2020-12-15 2023-06-30 Eurenco France Procédé d'obtention de structures à base de nitrocellulose par fabrication additive

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US12077653B2 (en) * 2019-03-15 2024-09-03 University Of South Alabama Build materials for photochemical additive manufacturing applications
IT201900005788A1 (it) * 2019-04-15 2020-10-15 Torino Politecnico Processo di produzione di propellente composito tramite deposizione e polimerizzazione foto-attivata per endoreattori a propellente solidi
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CN115806456A (zh) * 2022-11-23 2023-03-17 西安近代化学研究所 一种添加Co-MOF的光固化火药及其制备方法

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AU2017237636B2 (en) 2022-09-15
AU2017237636A1 (en) 2018-10-18
US20220274898A1 (en) 2022-09-01
CA3018640A1 (fr) 2017-09-28
BR112018069474B1 (pt) 2022-08-16
KR20180130103A (ko) 2018-12-06
BR112018069474A2 (pt) 2019-02-12
EP3433086A1 (fr) 2019-01-30
EP3222408A1 (fr) 2017-09-27

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