US20160280614A1 - Bismuth-based energetic materials - Google Patents

Bismuth-based energetic materials Download PDF

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US20160280614A1
US20160280614A1 US15/034,552 US201415034552A US2016280614A1 US 20160280614 A1 US20160280614 A1 US 20160280614A1 US 201415034552 A US201415034552 A US 201415034552A US 2016280614 A1 US2016280614 A1 US 2016280614A1
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compounds
salts
bismuth
energetic
soluble
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Jiri Nesveda
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Sellier and Bellot AS
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B35/00—Compositions containing a metal azide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B41/00—Compositions containing a nitrated metallo-organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
    • B60R2021/26029—Ignitors
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C9/00—Chemical contact igniters; Chemical lighters

Definitions

  • This invention relates to bismuth-based energetic compounds and the method of their preparation and usage.
  • Irreplaceability of salts of heavy, precious metals, just like lead with aromatic polynitro or other energetic compounds with acidic characteristics e.g. nitrogenous heterocyclic compounds—tetrazoles etc.—lies in the release of the vast amount of heat that is generated during the condensation of the vapours of these relatively low-boiling metals. This heat is then transferred in steps into a propellant charge in order, for example, to achieve the maximum efficiency of the heat transfer and the ignition temperature (T) required.
  • T ignition temperature
  • these explosives benefit from an extended ignition impulse and the generation of a sufficient quantity of condensed product with the highest heat capacity possible and in this manner the heat transfer efficiency is improved even more.
  • the primary explosives identified above are not able alone to full fill all requirements for reliable function of primer—they lack sufficient sensitivity to stab ignition, which is created by combining friction and impact, with the friction strongly prevailing, while some of them show too great brisance. That is the reason for the utilisation of additional auxiliary components—i.e. sensitising or friction agents that can be selected from 2 types of materials, either active or inert.
  • the active sensitising agents used may comprise other explosives with a substantially lower ignition temperature as compared to the default explosive. The friction between the crystals inside the default explosive during its puncturing by the anvil or by the stab releases a certain amount of heat and causing a local increase of the temperature (T), depending on the intensity of the heat outlet.
  • the primary explosive used is similar to tetrazene, the second of the above-mentioned principles comes to mind—the utilisation of an inert material with its grains dispersed evenly in the explosive and functioning as accumulators of the heat energy concentrated on their surface to once again induce a local increase of temperature (T).
  • T temperature
  • these must be high-melting compounds with a melting point greatly exceeding the ignition temperatures of the generally known explosives—i.e. at least 550° C., and therefore the compounds utilised must definitely be heat and thermally non-conductive.
  • ground glass is also problematical—there is a difference between the material obtained by the fragmentation of glass waste from glass plants—a method utilised by numerous ammunition factories—and a different material produced by grinding, using ball mills, which has a significantly more even structure together with a lower sensitising ability—resulting from its rounded corners and edges where energy concentrates.
  • crushed i.e. obtaining a sufficient amount of the material fraction required from the total amount of the waste.
  • This type of glass may additionally induce undesired activations, e.g. during drop tests of primers from lower fall heights.
  • the base material must comprise either an organic or an inorganic compound comprising molecules that include certain functional groups defined as “explophors”—i.e. explosibility carriers in the descriptions provided of contemporary explosives. It mainly comprises a combination of two or more electronegative elements with relatively wake bonds, i.e. their bonding energy is low; and these bring the whole molecule to a certain degree of instability that is called explosibility. Such compounds then offer the possibility for exothermal decomposition releasing Gibbs free energy and of forming more stable products with stronger bonds. This essential principle, derived from the principles of thermodynamics and of reaction kinetics, is applicable both to compounds and to explosive mixtures.
  • the functional groups mentioned above e.g. the nitro group —NO 2 , the nitroso group —NO, the hydrazino group —NHNH 2 , the hydroxyl amino group —NHOH, the nitramino group —NHNO 2 , the hydrazo group —HN—NH—, the azo group —N ⁇ N—, the azido group —N 3 , the diazo group —N 2 +, the furoxane group, etc., are common known and when combined with aliphatic as well as cyclic—aromatic or heterocyclic compounds, together they constitute hundreds of explosive compounds, then jointly referred to as “energetic materials”.
  • salts of inorganic or organic alkalis depends on their stability, which is directly proportional to the stability of the alkali.
  • Salts of weak alkalis such as ammonia, hydrazine or hydroxylamine
  • salts containing guanidine or its derivatives are highly stable and nowadays are at the height of their popularity.
  • Tens of patents have been filed during the past 20 years referring to the applicability of these compounds for use in propulsion systems—rockets, gas generators and modern azide-free airbag inflators. These compounds lack any characteristic of initial explosives however.
  • condensation products of some tetrazoles with aromatic polynitro compounds that were first patented in Germany in the year 1957. These are produced by the reaction of the alkaline salts of tetrazoles either with the chlorderivatives of organic polynitro compounds or with tetranitro-aniline. Examples include the sodium salt of 5-nitro-tetrazole or the disodium salt of 5,5′-bistetrazole reacting with either picryl chloride or styphnyl dichloride to produce 2-picryl-5-nitrotetrazole or styphnyl bistetrazole or dipicryl bistetrazole. Similar compounds are currently manufactured by the German company Dynitec. Their characteristics resemble those of explosives but they are used only for special applications.
  • Another group comprises compounds, in which tetrazoles play the role of a weaker or a stronger alkali and therefore these compounds are able to form salts with other explosive compounds with acidic characteristics—e.g. polynitrophenols, hydrazoic acid, perchloric acid and dinitramide.
  • acidic characteristics e.g. polynitrophenols, hydrazoic acid, perchloric acid and dinitramide.
  • These compounds are subjects of research by German scientists.
  • One starting point may be 5-amino tetrazole, for example; its acidity reduced by methylation to produce a 2-methyl or even a 2,4-dimethyl derivative.
  • the first of these is a weak alkali, only capable of forming salts with strong acids; the second is a strong alkali, able to form salts, even using weaker acids, to produce the relevant azides and dinitramides.
  • pentaamine(5-cyano-2H-tetrazolato-N2)cobalt(III) perchlorate or the similar BNCP, i.e. tetraamine-cis-bis(5-nitro-2H-tetrazolato-N2)cobalt(III) perchlorate.
  • Patents and patent applications from recent years include similar complex compounds but these are free of any undesired perchlorates with their central atom formed from one of the transition elements an making advantage of Co that forms such complex cations as the diatomic pentaamino cobalt azide or the positively monovalent pentaamino cobalt diazide or similar ions of pentaamino cobalt nitrate or of tetraamino cobalt dinitrate, forming salts with anions contained in such explosive tetrazole derivatives as 5-nitrotetrazole, 5-nitraminotetrazole, 5,5′-azotetrazole and even 5,5′-diazoaminotetrazole.
  • Examples of the resultant products may include any the following—pentaamine (azido) cobalt (III) azotetrazolate, pentaamine (azido) cobalt (III) nitrotetrazolate and pentaamine (azido) cobalt (III) nitraminotetrazolate.
  • These compounds contain cobalt, however, now, like nickel, they are ranked amongst the toxic elements. The sensitivity to friction manifested by these compounds is very low and thereby, in this respect, they are predestined rather for detonators and their application in primers could bring about serious problems—the need for extreme sensitisation.
  • the authors of the patent also refer to the simple metal salts of basic explosive tetrazoles (5-nitrotetrazole, 5-nitraminotetrazole, 5,5′-diazoaminotetrazole and 5,5′-azotetrazole) and those are the salts of Fe, Cu and Na.
  • the salts of Fe and Na are characterised by their very low sensitivity to friction once again, not to mention their variable content of crystal water (especially in Na salt), whereas the salts of Ca (primarily 5-nitrotetrazole and 5,5′-azotetrazole) are brisant primary explosives that pose a serious handling hazard. These compounds neither could be recommended for primer production.
  • any compositions based on these compounds must contain an extremely high amount of a sensitising agent—i.e. up to 47% of grown glass!
  • One example could be diammonium diaquatetrakis(5-nitro-1H-tetrazolato-N2) cuprate or ferrate.
  • diammonium diaquatetrakis(5-nitro-1H-tetrazolato-N2) cuprate or ferrate Similarly to other complex compounds, having a complex and very large molecula with a high content of organically bonded nitrogen acting in association with a balanced oxygen content to ensure high performance even with respect to large amounts of gaseous products.
  • reaction kinetics of such voluminous and complex molecules it should be assumed that these undergo a very complicated thermal decomposition, which is usually manifested by a reduced flame temperature.
  • these compounds do not have the heat transfer mechanisms mentioned above that are utilised during phase changes (condensation) of the fumes of low-boiling metals.
  • the invention is concerned to the production and the application of new energetic compounds based on bismuth salts that, with their lower level of toxicity, will be the best replacements for such primary explosives as lead tricinate, the characteristics of which are optimal for its particular purpose and that is basically viewed by experts as being an irreplaceable primary explosive.
  • this “irreplaceability” is mainly based on the presence of a heavy, more precious metal, which is bonded by a weak and easily cleavable bond to ensure a very efficient heat transfer mechanism.
  • the periodic system offers only a very limited selection, however there is still a metal that is ranked amongst the heaviest elements known and, in accordance with the modern criteria and compared to various other metals used in ammunition production, its toxicity is considered as being amongst the lowest values measured. That is bismuth (Bi), included in group 5.A of the periodic table, located in the same sub-group as the incomparably more toxic arsenic and antimony. As far as certain physical properties are concerned—i.e.
  • this element is similar to lead, its behaviour in its melted state when its specific gravity exceeding the value of its solid state level resembles rather arsenic, antimony or water in its solid state (ice), predestining this element for its application in special alloys that fill the mould perfectly, i.e. type metal, and in addition for the special low-melting eutectic alloys used in thermal fuses and for special solders.
  • Bi has found its way into ammunition production during the last few decades and has been used in special alloys for replacing lead shots and for bullet cores.
  • Bi in the form of vanadate has been utilised in non-toxic pigments, lubricants and even as a catalyst for the production of acrylic fibres, etc. It has also found extensive use in medicine, as a component of both historical and modern pharmaceutical and cosmetic products. So called the oxide salts (alkaline salts or sub-salts) of Bi, are uses for this purposes. They are compounds like (subnitrate, subcarbonate, subcitrate, subgalate and subsalycitate) are insoluble in water, for internal and external use as anti-diarrheal medication, for treating gastrointestinal illnesses, for internal or external infections, for peptic ulcers and for skin diseases.
  • X an anion of an inorganic acid (e.g. NO 3 —, Cl—, CIO4- or a remainder of an organic acid).
  • 1 mole of “a normal” bismuth salt creates 1 mole of an oxide (alkaline) salt and 2 moles of the corresponding acid.
  • the released acid cannot to acidify the solution to a sufficient level to maintain the Bi ions in a dissolved state and the Bi will therefore be precipitated, forming an alkaline (oxide) salt, which obviously makes it unusable for any further precipitation (e.g. certain explosive salts).
  • Any solution of a sufficient concentration suitable for practical application would require strong acidification but such an acidic solution would prevent precipitation or might even cause the decomposition of many compounds.
  • Positively bivalent penta-aquahydroxo complex Bi(H 2 O) 5 OH or anhydrous Bi(OH)(2+) 3.
  • One option would be to make use of the highly diluted solutions utilised in analytical chemistry—0.1-0.01%, whereby a sufficient level of acidification corresponds with approximately 0.1 M to keep the cations of Bi inside this solution to be precipitated using such compound forming Bi salt with sufficiently low solubility product (high pS). That enables the determination of Bi by gravimetrically means, e.g. as oxoformate, oxinate or pyrogallol salt. However, using such diluted solutions in the large scale process would not be efficient.
  • Analytical chemistry makes use of additional complex-forming agents, e.g. tartaric acid that bonds Bi ions into a soluble complex, and it is applied mainly in situations in which the precipitation is performed in a slightly acidic environment.
  • additional complex-forming agents e.g. tartaric acid that bonds Bi ions into a soluble complex
  • compounds of Bi can be prepared by simple dissolving metallic Bi, its oxide (Bi 2 O 3 ) or oxo-carbonate (BiO) 2 CO 3 in the corresponding acid; this applies mainly to salts of strong inorganic or organic acids.
  • the main subject matters of this invention process are identifying the Bi salt suitable for use as a multi-purpose precipitant, the optimisation of the precipitation methods for producing specific compounds and the description of these compounds in regard to their explosive properties.
  • this invention refers to bismuth oxo-perchlorate.
  • Bi salts of hydrazoic acid Bi salts in the default series of aromatic polynitrophenols—of picric acid (TNF), styphnic acid (TNR) and trinitro phloroglucinol (TNFG) and further 4,6-dinitroazidophenol (DNAF) and 4,6-dinitrobenzofuroxane (DNBF) together with Bi salts of selected explosive 1-H-5-substituted tetrazole derivatives.
  • the filtering property was improved by implementing the boiling precipitation method and an order for adding the solutions has been established to enable the precipitation to start from the most acidic environment possible in order to obtain the best possible crystalline products.
  • precipitation can obviously be implemented under various conditions in regard to the reaction temperature and the method of pouring the solutions required for the precipitation process. These methods can actually influence the manner in which the Bi bonds within the molecules use any of the above-mentioned cations. This may also have a certain impact on the explosiveness of the resultant compound which is dependent not only on the overall metal content within each molecule but also on the nature of the bonds, with respect to the energies necessary for their cleavage—activation energies.
  • the compounds were additionally subjected to thermal testing using the difference thermal analysis (DTA) method and their sensitivity to flame and friction by regular explosive testing.
  • DTA difference thermal analysis
  • Each of the compounds had to be matched with the optimal precipitation method selected for achieving the best filterable products. This is applicable mainly in cases in which the solubility of the precipitate is so low that it will fall-out in a colloidal state (i.e. salts of 5,5′-azo-tetrazole, 5,5′-diazoaminotetrazole, 5,5′-bis-tetrazolylhydrazine and salts of TNFG).
  • Azides and picrates are significantly more soluble and fall-out in an amorphous or a micro-crystalline form that enables good filtration.
  • the testing conducted during the differential thermal analysis (DTA) involved heating-up a 20 mg sample at the standard rate of 5° C./min. Processes not involving any explosions or detonations but instead just an exothermic reaction (in Bi salts of 5-nitraminotetrazole, 5,5′-bis-tetrazole, 4,6-dinitrobenzofuroxane and 4,6-dinitroazidophenol) were continued with the heating rate increased to 20° C./min. That always resulted in detonations, except for the Bi salt of 4,6-dinitrobenzfuroxane, which showed deflagration only, and the Bi salt of 4,6-dinitroazidophenol, which showed only strong exothermal peak.
  • DTA differential thermal analysis
  • Friction sensitivity was tested by smearing the compound using a pestle in a porcelain bowl. Unless initiated, the compound was considered as being insensitive to friction as compared to regular primary explosives. Most uninitiated compounds actually showed black trace right beneath the pestle, which signifies that the reaction occurs in there and that it is not transferred to any other remaining material.
  • Compounds exhibiting signs of frictional sensitivity e.g. Bi salts of 5,5′-azotetrazole and 5,5′-diazoaminotetrazole and 5,5′-bis-tetrazole and 5,5′-bis-tetrazolylhydrazine
  • PCT frictional sensitivity gauge
  • the frictional sensitivity is lower than that for TNRO and that is why these explosives can be considered as safer for handling.
  • the first two compounds in particular demonstrate their excellent functioning in any type of primer designated for centrefire or rimfire cartridges.
  • the frictional sensitivity test was performed by applying friction with a porcelain pestle subject to variable load in on porcelain plate containing several milligrams of the examined compound. This test is highly subjective and its results only make sense when they are compared with the tests of other compounds that have already been implemented and the frictional sensitivity of which is known and has been subjected to verification for many years. Owing to the fact that the common primary explosive that is considered to be the least sensitive to friction is tetrazene, that is initiated by the load of 900-1,000 g, the sensitivity of the compounds listed above has been evaluated with reference to tetrazene. Any compound with substantially lower frictional sensitivity is labelled with ⁇ , while any sensitivity that to a certain extent is comparable will be defined using the indication +.
  • potassium salt but this salt is incomparably more soluble and that could cause certain complications during the process of its separation from the solution and potassium salts should preferably also be excluded from any reactions involving the precipitation of perchlorate solutions because the precipitation from more concentrated solutions would cause excessive precipitation of the very little soluble potassium perchlorate.
  • the sodium perchlorate obtained from sodium salts in the course of a metathesis exchange at ambient temperature (T) is about 10-15 times more soluble at boiling temperature of its saturated solution. Immediately prior to the reaction the 5,5′-bis-tetrazolylhydrazine is converted into a soluble sodium salt.
  • the compounds mentioned above can be used in the same form as any other soluble salt, including metal salts and also the salts of certain organic or inorganic alkalis. In all these cases it is possible to use other alkaline metals such as lithium, caesium and rubidium. As far as salts of potassium, caesium or rubidium are concerned, the solutions used must be diluted more to avoid any undesired excessive precipitation of the less soluble perchlorates of these metals, while, on the other hand, perchlorates of all other metals are so soluble that their separation from the resultant compound can be carried out on a quantitative basis.
  • Salts of aromatic polynitrophenols can be prepared using the even more soluble alkaline earth salts (especially the salts of calcium, magnesium and strontium) and also the salts of some other metals, such as iron, nickel, cobalt and manganese.
  • the salts of tetrazole derivatives can be produced using any salt of an alkaline metal and also alkaline earth salts, except for the salts of 5,5′-azotetrazole which are the least soluble salts of these metals.
  • the above-mentioned tetrazoles can be obtained using salts or organic and inorganic alkalis such as hydrazine, guanidine and their amino derivatives.
  • 5,5′-azotetrazolate and 5,5′-bis-tetrazolate are stable pentahydrates, while 5,5′-diazoaminotetrazolate can be tetra- to pentahydrate and 5-nitrotetrazolate can be di- to tetrathydrate.
  • the table only refers to the salts of selected energetic compounds. There are obviously many other compounds from which it is possible to form explosive salts using method in accordance with this invention—i.e. those having one or more substitutable hydrogens—e.g. the salts of 4,6-dinitro-3-hydroxychinon diazonium, 4,6-dinitro-3-carboxychinon diazonium, 2,3,6-trinitro-p-azidophenol, 5-azidotetrazole and 5-hydrazotetrazole and others.
  • substitutable hydrogens e.g. the salts of 4,6-dinitro-3-hydroxychinon diazonium, 4,6-dinitro-3-carboxychinon diazonium, 2,3,6-trinitro-p-azidophenol, 5-azidotetrazole and 5-hydrazotetrazole and others.
  • Bi salts lie in their minimal solubility, so, as has been proven in practical experiments, these salts can be precipitated from aqueous solutions without any problem; this is even possible in regard to such compounds as 5-nitrotetrazole, for example, wherein the most significant problem lies in the excessive solubility of its salts as also applies to the salts of such metals as Pb and Ba.
  • the Bi salt will precipitate reliably and it will be expelled in an almost quantitative yield, which represents another irreplaceable advantage of Bi salts.
  • the most interesting property of explosive Bi salts is their capability of initiation by stab—i.e. the concentration of energy to the smallest possible point. Even the compounds that are not found to be sensitive to friction or to shock in accordance with the regular criteria leave a black trace of reaction products at the point of contact between the pestle and the porcelain bowl. The compounds that show sensitivity to friction are also the ones that are the most are stab sensitive, which is a direct prerequisite for their use in ammunition primers, for example.
  • primer composition When combined with the other generally known components of primer composition, such as non-toxic pyrotechnical oxidising agents (potassium nitrate, caesium nitrate, oxo-nitrates of Bi), non-toxic fuels (Al, Ti, Zr, B), energetic components (NC, PETN and other energetic materials) and frictionators comprising heat non-conductive materials with a high melting point (e.g. glass, sulphides of Bi), some of the compounds prepared will be ideal for application in non-toxic primer, detonator and general ignition compositions.
  • non-toxic pyrotechnical oxidising agents potassium nitrate, caesium nitrate, oxo-nitrates of Bi
  • non-toxic fuels Al, Ti, Zr, B
  • energetic components e.g. glass, sulphides of Bi
  • frictionators comprising heat non-conductive materials with a high melting point (e.g. glass, sulphides of Bi)
  • the compounds mentioned above are significant because of their high thermal and chemical stability and their resistance to moisture absorption. These are substantially less brisant explosives than other comparable already existing primary explosives such as dinol or TNRO. They still provide a sufficiently warm flame and also a long heat impulse, combined with an efficient heat transfer mechanism. That is why they are basically predestined for application as main primary explosives, especially those that show a sufficient degree of sensitivity to friction and primarily to stab, and for use in primers designated for centrefire and rimfire ammunition and for cartridges for sporting, hunting and also for military ammunition.
  • Compounds that are less sensitive to mechanical impulses can that be used as auxiliary energetic materials for primer compositions and for various types of ignition systems utilising pyrotechnical compositions, for squib for electric blasting caps and for airbags.

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  • Inorganic Chemistry (AREA)
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CZ2013-858A CZ305403B6 (cs) 2013-11-07 2013-11-07 Energetické materiály na bázi bismutu
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US11535575B2 (en) 2016-07-11 2022-12-27 Dynitec Gmbh Lead-free initiating agents or initiating agent mixtures
CN115896857A (zh) * 2022-12-30 2023-04-04 重庆大学 一种硫化铋-碳纳米材料及其制备方法和应用
CN116410229A (zh) * 2023-04-12 2023-07-11 西北大学 一种铋配合物及其制备方法和应用

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SI3164375T1 (sl) * 2014-07-03 2020-07-31 Ruag Ammotec Gmbh Pirotehnično vžigalno sredstvo

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EP3066054A1 (en) 2016-09-14
US11814332B2 (en) 2023-11-14
US20190152873A1 (en) 2019-05-23
RS61964B1 (sr) 2021-07-30

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