WO2012049660A1 - Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof - Google Patents
Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof Download PDFInfo
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- WO2012049660A1 WO2012049660A1 PCT/IB2011/054567 IB2011054567W WO2012049660A1 WO 2012049660 A1 WO2012049660 A1 WO 2012049660A1 IB 2011054567 W IB2011054567 W IB 2011054567W WO 2012049660 A1 WO2012049660 A1 WO 2012049660A1
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- C—CHEMISTRY; METALLURGY
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/08—Application of shock waves for chemical reactions or for modifying the crystal structure of substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01G23/047—Titanium dioxide
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- C01G25/02—Oxides
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
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- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention refers to a nanomaterial synthesis process from the decomposition and subsequent reaction among insoluble precursors, or precursors which hydrolyze in contact with water, incorporated in the internal phase of an emulsion, under the effect of a shock resulting from the emulsion detonation, thus allowing the process implementation in a wide range of nanomaterials .
- Nanomaterials inferior to lOOnm are constituent blocks of a new and recently emerging subject area, designated nanotechnology .
- nanotechnology is also frequently present in main world leaders' speeches. It is presented as holding the potential of providing a technological discontinuity with as relevant positive implications in citizen life as past historical events, such as the discovery of steam machines, the train, the automobile, the computer and biotechnology.
- Such enthusiasm is a result of particles or structures, such as films, pores or nanometric surfaces within a given material, presenting a group of electrical, optical, magnetic and mechanical properties, which are different from those of the same material having superior dimensions.
- This category comprises a group of methods already established or in industrialization imminence, namely: a) sol-gel, b) co-precipitation and c) hydrothermal and electrochemical synthesis.
- sol-gel a group of methods already established or in industrialization imminence
- co-precipitation a group of methods already established or in industrialization imminence
- hydrothermal and electrochemical synthesis have as common principle a starting material in solution or gel form, wherein precursors are either dissolved to a molecular scale or dispersed in the desired stoichiometric proportion.
- these precursors are decomposed in controlled manner, a precipitate being formed, usually as an hydroxide, which requires several subsequent treatment stages, such as calcination, for its conversion into an oxide with the desired crystalline structure, being followed by a final breakdown by grinding process.
- These methods comprise processes for both the production of individual nanoparticles and for direct application in surface coating, namely a) combustion synthesis, b) spray pyrolysis, c) evaporation/oxidation of metals, plasma, CVD, PVD, laser deposition, etc.
- these methods are based on the vaporization of the precursors introduced in a variety of solvents. After turning into the gaseous state, the chemical intended reaction among precursors occurs, followed by nanoparticle condensation, with the consequent heat release, which implies the inevitable and undesirable coalescence and coagulation stages of the formed nanoparticles, thus causing aggregate formation and therefore showing a major drawback of this method.
- this methodology is usually designated by "bottom-to-top” approach, that is, it starts from the individual molecule to a first stable structure.
- nanoparticles are usually prepared from a first slow reaction in the solid state among different precursors, such as carbonates, oxides etc. It is also designated “mechanosynthesis " , wherein the reaction activation energy is supplied by a mill, being followed by an intensive grinding process until particles inferior to 200 nm are obtained.
- the main limitations in this low-cost method besides the difficulties observed in obtaining dimensions inferior to 0.2 microns, are related to the presence of impurities, with a non-homogeneous particle- size distribution and essentially at a deficient homogeneity degree, especially when it comes to synthesizing composites and ternary structures or superior structures, originated by incomplete diffusion reactions among reagents. From a conceptual perspective, and unlike previous methods, this is a "top-to-bottom” approach wherein the starting point is a micrometric structure, whose dimension will be consecutively reduced by mechanical energy application.
- EP1577265 "Production of fine powder of aluminium oxide” discloses an industrial process for the production of micrometrical alumina from a cyclic detonation method of mixed granulated aluminum with an oxidizer, the later possibly being an emulsion (w/o) .
- This has distinct steps, including the previous preparation of a class-1 substance (explosive) and wet collection: it essentially implies feeding the granulate material into the reactor; being followed by the explosion; the products thus obtained passing to the wet chamber; subsequent cooling and final collection stage of the material.
- the process thus described differs from that described in the present invention in that the process is carried out in gaseous phase and does not include insoluble precursors, either stable or instable when in contact with water.
- WO2009040770 “Nanocrystalline spherical ceramic oxides, process for the synthesis and uses thereof” discloses a synthesis process for spherical micrometrical particles, with nanocrystalline structure, from the detonation of an emulsion (w/o) at a detonation temperature superior to the melting point of the oxides thus formed, allowing these to assume a spherical form.
- WO2009144665 “Nanometric-sized ceramic materials, process for their synthesis and uses thereof” discloses a method for nanomaterial synthesis, such as binary, ternary and higher oxides, nitrates and carbonates, from an emulsion (w/o) detonation at low temperatures (inferior to the ceramic nanomaterial melting point), with dissolution of soluble metallic precursors in oxidizing phase (internal), or from the addition of soluble propellants to the external phase or addition of metals or metal alloys, after emulsion formation.
- Xinghua Xie et al discloses a process for obtaining ZnO and Li 2 0 nanoparticles from the detonation of an emulsion, in which lithium and zinc nitrates were dissolved in the internal phase. This emulsion is later ignited by a no .8 detonator, placed inside a military explosive (RDX) .
- RDX military explosive
- this is a synthesis method exclusively carried out in gaseous phase and mainly using soluble precursors in oxidizing phase of the emulsion, which also resorts to the use of explosive material (class 1), RDX and detonators.
- This process differs from the technical characteristics of the solution described by the present invention in that it is carried out in gaseous phase and does not include insoluble precursors, either stable or instable when in contact with water .
- the process of the present invention is generally within the scope of "solid-phase methods” and aims at overcoming the limitations associated with this category of methods, namely: difficulty in obtaining dimensions inferior to 0.2 microns, impurities present in the emulsion, time-consuming reaction times and low homogeneity degree in composites or ternary structures, due to incomplete diffusion reaction among reagents, upholding the use of common and cheap insoluble precursors, such as carbonates and metallic hydroxides .
- the present invention refers to nanomaterial synthesis in solid phase, in which reaction is induced by a shock from the detonation of an emulsion, wherein insoluble precursors were previously fed.
- the process of the present invention is based on endothermic decomposition and subsequent reaction among water-insoluble precursors present in the emulsion.
- insoluble precursor represents a set of compounds exhibiting one of two characteristics:
- energy Since being precursors, whose decomposition is an endothermic process, energy must be provided in order to actuate the desired reaction. So being, in the present method, energy is provided by the Shockwave caused during detonation of the emulsion wherein precursors were previously added.
- a detonation reaction speed between 4000-6000 m/s causes pressures between 50,000-115,000 bar at the reaction front, respectively, which will compress the precursors and consequently actuate an interruption of their chemical connections and subsequent reaction, thus resulting in the formation of the intended solid state nanomaterial.
- the resulting nanoparticles separate very quickly at the hot reaction zone oriented by gases from the detonation which scatter in a radial direction at high speed rates.
- the process of the present invention also uses common water- insoluble solid precursors as starting material, such as hydroxides, oxides, carbonates, or compounds which hydrolyze in contact with the water, such as carboxylates and metal alkoxides etc., the process being therefore applicable within a new sub-category of high-pressure solid-phase methods.
- common water- insoluble solid precursors such as hydroxides, oxides, carbonates, or compounds which hydrolyze in contact with the water, such as carboxylates and metal alkoxides etc.
- the nanomaterial is the result of thermal decomposition and subsequent reaction among starting precursors, induced by the shock wave of an emulsion detonation, to which the insoluble solid precursors were previously fed into the internal phase, in other words, by endothermic decomposition reaction in the solid state, the precursors do not react in the so-called reaction front, thus not providing any gaseous species supporting the Shockwave progress.
- the conversion reaction in the nanomaterial with the intended structure only occurs subsequently to the Chapman-Jouget point (C,J), during the isentropic expansion of the gases. Since occurring at extremely high pressures between 50,000 - 115,000 bar, this solid-phase reaction provides a set of advantages in terms of mechanosynthesis , both at a procedural level and in terms of the final properties of the obtained materials, namely:
- Nanomaterial with high-pressure production properties such as nanocrystallinity, the amorphism, alteration of phase diagram or emergence of unique crystalline phases ;
- the process according to the present invention aims at obtaining a multiplicity of nanomaterial in the form of composites or binary, ternary structures or superior structures, with homogeneous primary particles of small dimension from a solid-state reaction among starting insoluble precursors.
- the method herein proposed comprises the following stages (Fig.l): a) Preparation of the emulsion, wherein the precursor selection is included in stoichiometric amounts, and the incorporation thereof in the internal phase of the emulsion, preparation of the external phase, and the emulsification of both phases; b) Sensitizing of the emulsion a) , preferably by incorporating hollow silica, polymeric, gasification spheres or any other method known in the art;
- the synthesis emulsions prepared according to the present invention are categorized in two types:
- melt/oil m/o
- the emulsions should preferably comprise an ammonium nitrate-based and oxygen-rich internal phase, and a propellant external phase formed by hydrocarbon derivatives.
- the external phase is added with a surfactant reducing the surface tension among both phases, thus allowing their subsequent emulsification .
- the nanomaterial precursors meant for inclusion in the emulsion are selected from a group of water-insoluble solids, such as hydroxides, oxides, carbonates, or insoluble compounds which hydrolyze when in contact with water, such as carboxylates or alkoxides.
- the relative amounts and proportions thereof are determined by the empirical formula of the intended end compound and chemical reaction stoichiometry; by means of these two parameters, it is possible to calculate the required amount per precursor for the formation of the intended composition.
- the total amount of precursors in the emulsion should be inferior to 70% in weight of its overall composition, so as to guarantee the existence of sufficient energy for the progression and support of the detonation reaction .
- Viscosity is an essential parameter for the process of the present invention to take place, whilst assuring the stability of the emulsion along the several processing stages.
- This property is related to the physical state under which ammonium nitrate is fed into the emulsion and which might adopt two different forms, giving rise to two distinct emulsion concepts : a) Water-in-oil (w/o) emulsion, wherein the solid ammonium nitrate is previously dissolved in water, forming an aqueous solution at about 105°C, being subsequently emulsified with the external phase (propellant) within an emulsion.
- This kind of emulsion is formed whenever the selected precursors are stable when contacting with water, such as hydroxides, carbonates, oxides etc. (Fig.2) .
- This kind of emulsion is preferably used whenever the selected precursors decompose in the presence of water/moist, such as alkoxides, carboxylates, organometallic compounds etc. (Fig.3).
- the compounds meant to be added to ammonium nitrate, for the purposes of decreasing its melting point and which should also be water-insoluble (propellants ) may be selected among inorganic salts, alcohols or compounds such as glycine, succinic acid, urea, etc..
- Urea is one of the preferred compounds, for the purposes of the present invention, once they comply with all criteria mentioned.
- the external phase being the one responsible for determining the general physical and chemical characteristics of the emulsion, its adequate selection and preparation is highly decisive for the compliance with a set of requirements inherent to the present invention: a) The emulsion should be detonated inside the reactor, without a housing, so as to avoid that the pyrolysis thereof results in the presence of contaminant substances in the final nanomaterial .
- the final rheology of the emulsion should present a significantly high consistency, with a viscosity superior to 200,000 cps assuring the composition support and necessary self-confinement so as to guarantee a stable detonation.
- the emulsified composition should have a relatively low viscosity / consistency during the first stages of the process, so as to guarantee its simple processing (emulsification, pumping, air injection, etc . ) .
- it must be formed in different geometries: cylindrical, planar, or spherical.
- the external phase of the emulsion is preferably based on hydrocarbon derivatives, for example waxes such as paraffinic or microcrystalline waxes, among others, or mixtures of waxes with mineral oils or mineral waxes with polymers, which, upon heating and liquefaction, have extremely low viscosity indexes (between 4 and 20 cps at 40°C), thus assuring a simple formation of the emulsion and processing thereof, and which upon sudden cooling change into the solid state, thus providing high consistency to the emulsion, which is an important requirement for the detonation stage, exempt from any pre-forming housing.
- hydrocarbon derivatives for example waxes such as paraffinic or microcrystalline waxes, among others, or mixtures of waxes with mineral oils or mineral waxes with polymers, which, upon heating and liquefaction, have extremely low viscosity indexes (between 4 and 20 cps at 40°C), thus assuring a simple formation of the emulsion and processing thereof, and which
- paraffinic waxes with low melting point are used, once they allow operating within a large temperature range between 65-95°C, in liquid state, also allowing carrying out all processing stages required for the preparation of internal/external phases, emulsification, etc., with low viscosity indexes.
- Emulsification Water-in-oil (w/o) or melt/oil (m/o) matrix emulsion is prepared from the emulsification obtained in internal and external phases of the emulsion, under mechanical energy effect within a equipment such as a static mixer, a jet mixer, or colloid mill.
- the internal phase is aqueous and oxygen-rich
- the external phase is propellant consisting of paraffinic waxes or mixtures thereof with mineral oils, to which a surfactant was previously added, which enables a decrease on surface tension among both phases.
- micelles In order to obtain a stable emulsion, micelles must have a size distribution from 1 to 10 microns and a 60, 000 to 100,000 cps viscosity at 85°C.
- the emulsion sensitization is usually carried out by adjusting its final density to a value inferior to 1.30 g/cm 3 , by adding a group of substances which feed and disperse a great number of microspheres thereinto. Such feeding may occur by direct injection and homogenization of a gas by chemical reaction, or by adding solid particles which retain the gas in its interior.
- microspheres when adiabatically compressed under mechanical energy or external pulse, form a group of "hot points" achieving about 400-600°C within them. This stage is carried out in a significant short time, among 10 ⁇ 3 to 10 ⁇ 5 s, actuating and supporting the detonation progress along the emulsion, at a speed superior to 4000 m/s.
- the detonation ignition in the emulsion may be actuated from a detonator or any other system with similar effects, such as capacitive or laser discharge etc.
- the Shockwave requires a length as long as two to five times its diameter (in the case of a cylindrical geometry) , in order to stabilize at a speed superior to 4000m/s. Therefore, another emulsion (w/o) is preferably prepared, designated base or ignition emulsion, which is bound to the emulsion containing the precursors and mainly consisting of ammonium nitrate and water in the internal phase, and mineral oil and emulsifying agent in the external phase, so as to avoid contaminant solid formation.
- This base or ignition emulsion should have a positive oxygen ratio, having a length as long as two to five times its diameter, so as to guarantee that the Shockwave is completely stabilized at a level superior to 4000m/s, when achieving the second emulsion, the synthesis emulsion (containing the precursors) assuring that no non-homogeneity occurs during the synthesis of the nanomaterial .
- This first emulsion (base or ignition emulsion) preferably comprises :
- ammonium nitrate 70-80%
- Emulsifying agent 0.75-1.5%
- the detonation ignition in the process of the present invention may be actuated by laser or capacitive discharge. Depending on the sensitivity of the emulsion composition, it might be directly ignited or ignited by another non-contaminating and more sensitive emulsion (ignition emulsion) , which provides the necessary shock energy to detonate the emulsion of the present invention.
- ignition emulsion another non-contaminating and more sensitive emulsion
- the detonation ignition in the synthesis emulsion is accomplished by means of an ignition emulsion.
- Dust is dragged by incoming gases from the detonation reaction into an expansion chamber, in which is preferably wet collected, so as to avoid dust accumulation in the air. Following, the collected material is sieved, dried at a temperature constantly inferior to 70°C and finally deagglomerated and housed.
- the process of the present invention allows obtaining nanomaterial with single (one element), binary (two elements), ternary (three elements) structures or higher, as well as composites (combinations of two different nanomaterials ) , with surface areas superior to 10 m 2 /g and consisting of primary particles between 5-80 nm.
- These properties are obtained from the Shockwave along the emulsion, whose effect actuates the following mechanisms, almost simultaneously: a) Decomposition and fragmentation of the soluble precursors, with conversion of the respective oxide; b) Reaction among several oxides, in order to form the intended final compound;
- Figure 1 shows the set of stages for nanomaterial synthesis (internal phase and external phase) for obtaining of the emulsion and subsequent stages for nanomaterial synthesis.
- Figure 2 shows the preparation stages of the synthesis emulsion's internal phase with stable insoluble precursor incorporation in contact with water, such as carbonates, hydroxides, or oxides and wherein the external phase consists of a mixture of paraffinic waxes, mineral oils and an emulsifying agent.
- Figure 3 shows the preparation stages of the synthesis emulsion's internal phase with stable insoluble precursors which hydrolyze and decompose in the presence of water, such as alkoxides, carboxylates and organometallic compounds and wherein the external phase consists of a mixture of paraffinic waxes, mineral oils and an emulsifying agent.
- the process for obtaining nanometric material is started by selecting the insoluble precursors in the adequate stoichiometric proportion, as well as the remaining components of the synthesis emulsion, and by preparing the ignition emulsion. 1. Emulsion preparation
- This emulsion is started by dissolving ammonium nitrate in demineralized water, within a stirring and heated tank, an ammonium nitrate solution (internal phase) being thus formed. Following, the internal phase emulsification occurs, by means of a mineral oil and emulsifying agent mixture (external phase) , inside an emulsifier, an emulsion matrix being obtained. Finally, 0.5% polymeric microspheres are added into a plastic tank at a low stirring rate, so as to provide an emulsion which is more sensitive to a detonator or any other type of ignition system (laser or capacitive discharge).
- the ammonium nitrate is: a) Dissolved, in case of precursors compatible with water, such as carbonates, oxides and hydroxides, in demineralized water, at a concentration about 80-90% and heated until a temperature between 95-105°C superior to the crystallization temperature of the mixture is achieved, so as to form a fully transparent solution exempt from visible crystals. b) Mixed with a compound which reduces its melting point, being followed by a slow and gradual heating with steam, until a temperature of 110 °C and the liquid state are achieved.
- the selected precursors are added to the ammonium nitrate in aqueous solution or liquefied, in stoichiometric proportions according to the crystalline structure intended for the nanomaterial meant to be synthesized, the mixtures being held under stirring so as to guarantee their homogeneity .
- the external phase or propellant is prepared by previous melting hydrocarbon derivatives, such as mineral oil and/or waxes, such as paraffinic or microcrystalline waxes among others, wax mixtures with polymers, preferable a paraffinic wax, having a melting point between 40-70 °C, and subsequent mixture with an emulsifying agent, an HLB (hydrophile /lipophil), which is suitable for the formation of the water in oil emulsion (w/o) .
- the external phase generally represents about 2-30% of the emulsion composition .
- the emulsification of the internal phase of the emulsion, in an emulsified matrix is carried out in a known emulsifier. Subsequently, the matrix is refined at about 60-150 psi, by passing the emulsion through restrictor static mixers.
- an organic sensitizer is carried out (0.2 to 2%), such as expanded polystyrene or contaminant-free polymeric spheres, or by adding and homogenizing air inside the emulsion structure, which is assured by passing the air/emulsion mixture through a static mixer.
- Dust is dragged by incoming gases from the detonation reaction into an expansion chamber, in which it is preferably wet collected, so as to avoid dust accumulation in the air. Following, the collected material is sieved, dried at a temperature constantly inferior to 70 °C and finally deagglomerated and housed.
- the nanomaterial obtained by the present method is characterized by: a) Multiple crystalline structures:
- Binary such as: cubic, hexagonal, Fluorite, Rutile, etc;
- Ternary such as: spinel, Perovskite, calcite, olivine, etc;
- a first emulsion designated emulsion 1, or ignition emulsion, which is responsible for the detonation reaction stabilization, being followed by emulsion 2 or synthesis emulsion, containing the composition comprising the different precursors.
- emulsion 1 50g of emulsion 1 were used, the same having subsequently been completed with about 400 g emulsion 2.
- Example 1 Preparation of emulsion 1 or ignition emulsion
- Plastic sensitizer polymeric spheres: 0.5%
- Emulsion 1 is prepared by dissolving NH 4 NO 3 in demineralized water within a stirred and heated tank, an ammonium nitrate solution being formed - internal phase. Then, the internal phase emulsification is carried out with a mixture of paraffinic wax and emulsifying agent (external phase) , heated up to 75 °C, within an emulsifier adequate to the viscosity range, an emulsified matrix being thus obtained.
- Example 2 Synthesis of nanometric cubic zirconia, stabilized with yttria 8Y (8 mol) , from insoluble precursors fed into the internal phase of the emulsion.
- Solid ammonium nitrate (99.9% purity) is dissolved in demineralized water at a 88% concentration, in a stainless steel tank heated with steam, the mixture being stirred at a temperature of about 98°C, so that a complete clarified solution is obtained (exempt from crystals).
- the pH value of the solution is adjusted with ammonium carbonate up to a value between 5 and 6.
- the zirconium carbonate 25% and yttrium carbonate 3.75% solid precursors are added, the heating with steam being maintained until the solution is restored to 98°C. The preparation of the internal phase will then be complete.
- the preparation is based on melting a paraffinic wax (representing 70% in weight of the external phase) having a melting point at 56 °C, followed by a temperature increase up to 65°C, a PIBSA-based emulsifying agent (Polyisobutylene Succinic Anhydride) being then added (30% in weight of total external phase) .
- a paraffinic wax having 70% in weight of the external phase
- a PIBSA-based emulsifying agent Polyisobutylene Succinic Anhydride
- the internal phase is firstly placed in an emulsifier tank having slow stirring and an external sleeve heated up to 85°C. Continuously, the external phase is slowly and at a constant pace added and maintained under stirring so as to avoid solid carbonate deposition. When addition is complete, the necessary mechanical energy is applied to the emulsion ( 700 rpm) for 5 min, until a 80, 000 -100, 000 cps viscosity is achieved.
- polymeric spheres are added tank at a significantly low stirring rate, so as to a 1.05 g/cm 3 density, followed by pre-forming and cooling stages for a 35 mm cylinder geometry, so provide an emulsion having the required consistency, avoids the use of a housing.
- a no. 8 detonator is applied to the 400g of the synthesis emulsion, having a cylindrical geometry and high consistency, in order to actuate the detonation.
- Table I shows a summary of the procedural parameters and the nanometric properties of cubic zirconia.
- Solid ammonium nitrate (99.9% purity) is dissolved in demineralized water at a 88% concentration, in a stainless steel tank heated with steam, the mixture being stirred at a temperature of about 98°C.
- the pH value of the solution is adjusted with ammonium carbonate up to a value between 5 and 6.
- Manganese carbonate 17.3% and lithium carbonate 2.77% are added, the heating with steam being maintained until the solution is restored to 98°C, the preparation of the internal phase being then complete.
- the internal phase is firstly placed in an emulsifier tank having slow stirring and an external sleeve heated up to 85°C. Continuously, the external phase is slowly and at a constant pace added and maintained under stirring so as to avoid solid carbonate deposition. When addition is complete, the necessary mechanical energy is applied to the emulsion ( 700 rpm) for 5 min, until a 80, 000 -100, 000 cps viscosity is achieved.
- polymeric spheres are added tank at a significantly low stirring rate, so as to a 1.15 g/cm 3 density, followed by pre-forming and cooling stages for a 35 mm cylinder geometry, so provide an emulsion having the required consistency, avoids the use of a housing.
- a solid ammonium nitrate (99.9% purity) and urea (99.9% purity) mixture is heated with steam in a stainless steel tank at about 110°C, the mixture being held under stirring. Titanium isopropoxide in liquid state it finally added and homogenized. The preparation of the internal phase is complete .
- the external phase is prepared as in examples 2 and 3.
- the emulsification is prepared as in examples 2 and 3.
- polymeric spheres are added into a tank at a significantly low stirring rate, so as to obtain a 1.15 g/cm 3 density, followed by pre-forming and sudden cooling stages for a 35 mm cylinder geometry, so as to provide an emulsion having the required consistency, which avoids the use of a housing.
- Table I shows a summary of the procedural parameters and the nanometric T1O 2 properties
- Example 2 shows solid insoluble precursor feeding into the internal phase of the emulsion so as to provide a ZrC> 2 binary structure having a nanometric primary particle size around 15 nm, not resorting to any ignition emulsion.
- Example 3 shows the capability of the several insoluble precursors (carbonates), existing within the internal phase, to synthesize a ternary structure under detonation wave effect.
- Example 4 depicts the capability of the detonation emulsion, having a water-free composition in the internal phase, to include precursors which hydrolyze with water (alkoxides), thus allowing its decomposition in the intended oxide (T1O 2 ) to occur only at a subsequent stage by detonation wave effect.
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KR1020137012585A KR20130140726A (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
EA201390371A EA201390371A1 (en) | 2010-10-15 | 2011-10-14 | METHOD OF SYNTHESIS OF NANOMATERIALS BY RECEPTION AND DETONATION OF EMULSION, PRODUCTS AND EMULSION |
CN201180049621.3A CN103201027B (en) | 2010-10-15 | 2011-10-14 | By the preparation of emulsion and the method for Explosive detonation nano material and products thereof and emulsion |
MX2013004189A MX2013004189A (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof. |
SG2013018924A SG188997A1 (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
JP2013533320A JP6019029B2 (en) | 2010-10-15 | 2011-10-14 | Method for synthesizing nanomaterials by preparation of emulsion and explosion, and emulsion |
CA 2814612 CA2814612A1 (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
US13/879,579 US9115001B2 (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
BR112013009169A BR112013009169A2 (en) | 2010-10-15 | 2011-10-14 | nanomaterial synthesis process from the preparation and detonation of an emulsion, its products and emulsions used. |
EP11788229.0A EP2627440A1 (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
AU2011315099A AU2011315099B2 (en) | 2010-10-15 | 2011-10-14 | Process for nanomaterial synthesis from the preparation and detonation of an emulsion, products and emulsions thereof |
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US9050604B1 (en) | 2014-06-06 | 2015-06-09 | LLT International (Ireland) Ltd. | Reactor configured to facilitate chemical reactions and/or comminution of solid feed materials |
US9452434B1 (en) | 2015-04-17 | 2016-09-27 | LLT International (Ireland) Ltd. | Providing wear resistance in a reactor configured to facilitate chemical reactions and/or comminution of solid feed materials using shockwaves created in a supersonic gaseous vortex |
US10427129B2 (en) * | 2015-04-17 | 2019-10-01 | LLT International (Ireland) Ltd. | Systems and methods for facilitating reactions in gases using shockwaves produced in a supersonic gaseous vortex |
US10434488B2 (en) | 2015-08-11 | 2019-10-08 | LLT International (Ireland) Ltd. | Systems and methods for facilitating dissociation of methane utilizing a reactor designed to generate shockwaves in a supersonic gaseous vortex |
CN105749809B (en) * | 2016-03-29 | 2018-01-09 | 中国科学院电工研究所 | A kind of device using Metal Explosion effect diamond synthesis crystal |
CN106748589B (en) * | 2016-11-30 | 2018-07-03 | 安徽理工大学 | Emulsion Compound sensitizer containing energy and preparation method thereof |
CN109128219A (en) * | 2018-09-30 | 2019-01-04 | 大连理工大学 | A kind of method that Gaseous Detonation method synthesizes carbon-based cobalt-copper alloy nano material |
CN112010719B (en) * | 2019-05-29 | 2021-11-30 | 南京理工大学 | Aluminum-containing explosive and preparation method thereof |
CN116217311B (en) * | 2022-12-19 | 2024-03-15 | 本溪钢铁(集团)矿业有限责任公司 | Method for debugging and sensitization of emulsion explosive formula by using Gibbs function variable |
CN116425601A (en) * | 2023-04-27 | 2023-07-14 | 中北大学 | Emulsion explosive for preparing barium titanate by explosion synthesis method and preparation method thereof |
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Publication number | Publication date |
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PT105339A (en) | 2012-04-16 |
EA201390371A1 (en) | 2013-08-30 |
CN103201027A (en) | 2013-07-10 |
WO2012049660A4 (en) | 2012-07-19 |
EP2627440A1 (en) | 2013-08-21 |
BR112013009169A2 (en) | 2016-07-26 |
CA2814612A1 (en) | 2012-04-19 |
JP6019029B2 (en) | 2016-11-02 |
AU2011315099B2 (en) | 2015-07-16 |
US20130224488A1 (en) | 2013-08-29 |
JP2014501601A (en) | 2014-01-23 |
CN103201027B (en) | 2015-08-19 |
SG188997A1 (en) | 2013-05-31 |
MX2013004189A (en) | 2013-08-08 |
US9115001B2 (en) | 2015-08-25 |
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