WO2006082844A1 - ナノサイズ粉体の製造方法 - Google Patents
ナノサイズ粉体の製造方法 Download PDFInfo
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- WO2006082844A1 WO2006082844A1 PCT/JP2006/301650 JP2006301650W WO2006082844A1 WO 2006082844 A1 WO2006082844 A1 WO 2006082844A1 JP 2006301650 W JP2006301650 W JP 2006301650W WO 2006082844 A1 WO2006082844 A1 WO 2006082844A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/363—Mixtures of oxides or hydroxides by precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/229—Lanthanum oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Definitions
- the present invention relates to a method for producing a nano-sized powder by nano-explosive synthesis capable of producing a ceramic powder or a metal and ceramic composite powder having a single component or multi-component force. Is.
- Nano (nm) size powders with single or multi-component forces are mechanical, chemical, thermal, catalytic, electronic, electrical, communication, optical, bio-medical It is required as a material for goods and consumer goods, ie, as a structure.
- a material for goods and consumer goods ie, as a structure.
- examples of such a material include ceramic nanopowder, or a composite powder of metal and ceramic obtained by modifying or mixing a metal with the ceramic nanopowder.
- devices using single- or multi-component nano-sized ceramic nanopowders or metal and ceramic composite powders are even better, more reliable, faster and easier to carry. That is required.
- nano-sized powders are obtained by using a so-called wet chemical etching method from an aqueous solution and Z or a non-aqueous solution to all or the following steps (1) to (6). It was synthesized after a part (see Non-Patent Documents 1 to 9).
- Powder that also has intermediate strength obtained by precipitation or the like during washing and drying in (4) above The body is deagglomerated, ie, atomized.
- FIG. 12 is a schematic diagram of a two-component powder 50 synthesized by a conventional wet-chemical method. Nucleation, growth, and agglomeration of the first component 51, followed by strong agglomeration, takes place within a few seconds under very mild conditions. At the same time, nucleation of the second component 52 usually starts over time at higher temperatures and sometimes requires a different pH. This co-precipitation end product 50 is strongly agglomerated and is a compound with non-uniform nanocrystalline properties. It consists of agglomerated agglomerates.
- FIG. 12 shows a case where agglomerates 53 and 54 of the first and second components are generated. In order to reach the final solid solution, this strong multi-component agglomerate needs to be treated at a higher firing temperature. To increase the density using this powder, high temperature and long sintering time were required.
- preparation methods include sol-gel methods, hydrothermal methods, inert gas concentration methods, aerosol decomposition methods via salts, ultrasonic chemistry (sonochemistry) or various precursor aqueous solutions (or non-aqueous solutions) via microwaves. ) Decomposition and combustion synthesis methods.
- the conventional combustion synthesis method is a method that can be produced in a short time, and has the advantage of saving energy and time.
- This rapid and simple manufacturing process is relatively homogeneous and can be used to produce high purity and crystalline acid ceramic ceramic powders (see Non-Patent Document 10).
- Alumina acid-aluminum
- titanium titanium oxide
- other nano-sized powders can be used for the synthesis of a wide range of particle sizes (see Non-Patent Document 11)
- Factors affecting this synthesis reaction include the type of fuel, the ratio of fuel to oxidant, the water content of the precursor mixture, and the mechanism of the combustion reaction is complex.
- Microscopic small single crystals i.e. crystallite size, specific surface area, agglomerate size and strength of the agglomerate, are primarily caused by enthalpy or combustion. Dominated by flame temperature. This flame temperature is the ratio of fuel properties to fuel Z oxidant. Depends on the rate. If a large amount of gas is generated suddenly during combustion, the heat of the process is wasted, the temperature rise is limited, and the probability of local sintering between primary particles is reduced. In addition, the generation of gas sometimes limited the contact between the particles and helped to produce agglomerates without strong agglomeration.
- Non-Patent Document 1 Z. Tianshu et al, Solid State Ionics, Vol.148, p.567 (2002)
- Non-Patent Document 2 T. Zhang et al., Solid State Ionics, Vol.167, p.191 (2004)
- Non-Patent Document 3 M. Kamruddin et al., Scripta Materialia, Vol.50, p.417 (2004)
- Non-Patent Document 4 JG Li et al., Solid State Chem, Vol.168, p.52 (2002)
- Non-Patent Document 5 T. M. Tillotson et al "J. of Non-Crystall Solids, Vol.225, p.358 (1998)
- Non-Patent Document 6 T. Tillotson et al., J. of Non-Crystall Solids, Vol.285, p.338 (2001)
- Non-Patent Document 7 S. Dikmen et al., Solid State Ionics, Vol.126, p.89 (1999)
- Non-Patent Document 8 J.S. Lee et al., Mater. Letters, Vol.58, p.390 (2004)
- Non-Patent Document 9 0. Vasylkiv and Y. Sakka, J. Am. Ceram. Soc, Vol.84, pp.2489— 2494 (2001)
- Non-Patent Document 10 R.M.G.A.Kinami and M.R.Morelli et al "Am. Ceram. Soc. Bull., P.67 (2000)
- Non-Patent Document 11 T. Mimani and K.C. Patil, Mater. Phys. Mech. Vol.4, pp.134-137 (2 001)
- Non-Patent Document 12 K.C. Patil, S.T.Aruna and T. Mimani, Curr. Op.Solid State Mater.Sci., Vol.6, p.507 (2002)
- Non-Patent Document 13 DA Fumo et al., Mater. Res. Bull, Vol. 31, p. 1243 (1996)
- Non-Patent Document 14 S. Bhaduri, SB Bhaduri and E. Zhou, J. Mater. Res. Vol .13, p.156 (
- the conventional method for producing a powder material such as ceramic by a combustion synthesis method has a problem that only agglomerated powder can be obtained and nano-sized powder cannot be realized.
- the nano-sized powder of sub-micron or less particularly, the ultra fine ceramic nano powder or the metal obtained by modifying or mixing the metal with the ceramic nano powder. And it is difficult to produce ceramic composite powder.
- an object of the present invention is to provide a method for producing nano-sized powders by nano-explosive synthesis that can produce metal and ceramic composite powders with high reproducibility.
- the first method for producing a nano-sized powder of the present invention is to chemistry a single or multi-component precursor agglomerate from a medium in which the raw material of the powder is melted.
- the precursor agglomerates containing explosive compounds by saturating the precursor agglomerates with explosive compounds or impregnating the explosive compounds at the nano-level during precipitation
- the raw material power of the powder also includes an explosive compound when the precursor agglomerate is precipitated, and the precursor agglomerate containing the explosive compound is exploded.
- the impact of high-energy explosion waves causes agglomeration of agglomerates due to a complex explosion, and nano-sized powders can be produced with good reproducibility.
- the second method for producing a nano-sized powder of the present invention it is possible to determine whether the powder raw material
- a precursor agglomerate having a single or multi-component strength is precipitously precipitated, and a nano-sized explosive compound prepared in advance is immersed in the precursor agglomerate, so that a precursor containing an explosive compound is contained.
- a first step of preparing an agglomerate and a second agglomerate containing a nano-sized explosive compound that is washed and dried while maintaining its component and morphological homogeneity A single or multi-component force is created by heating the process and a precursor agglomerate containing dried nano-sized explosive compounds at a heating rate sufficient to explode at the nanoscale.
- a third step of obtaining a nanosize powder is
- the precursor agglomerate is first chemically precipitated from the raw material of the powder, and the nano-sized explosive compound prepared beforehand is immersed in the precursor agglomerate.
- the impact of a high-energy explosion wave causes agglomeration of the agglomeration due to a complex explosion, reproducing nano-sized powder. It can be manufactured with good performance.
- the nano-sized powder is heat-treated.
- the explosion product can be further removed from the obtained nano-sized powder, and the homogeneity of the powder composition and the improvement of the powder form can be achieved.
- the explosive compound is preferably any of cyclotrimethylene tri-tolamine, tri-tolutoluene (TN T), nitroglycerin, and glycerin.
- the raw material of the powder is preferably a metal or a salt containing a metal.
- the metal is preferably a rare earth element such as cerium, gadolinium, lanthanum, conolt, nickel, manganese, zinc, norium, titanium, vanadium, niobium, tantalum, tungsten, molybdenum, magnesium, calcium, yttrium, di-
- a rare earth element such as cerium, gadolinium, lanthanum, conolt, nickel, manganese, zinc, norium, titanium, vanadium, niobium, tantalum, tungsten, molybdenum, magnesium, calcium, yttrium, di-
- the noble metal elements such as ruthenium, hafnium, aluminum, lead, copper, tin, scandium, indium, silicon, iron, strontium, gold and platinum, or a combination of these metals.
- the anion forming the salt is preferably any of nitrate ion, hydrochloric acid ion, sulfate ion, oxalate ion, acetate ion, oxyhydroxide ion, and hydroxide ion.
- the nano-sized powder preferably also has a ceramic force.
- the nano-sized powder is preferably composed of a metal in which a nano-sized metal is mixed with ceramic and a ceramic composite powder.
- a metal or multi-component metal oxide powder that is, a nano-sized ceramic powder can be synthesized in a very short time.
- a nano-sized ceramic powder in which dopant oxide is dissolved in metal oxide powder can also be synthesized.
- Sarako can also synthesize metal oxides modified with metals, ie, metal and ceramic composite powders. The invention's effect
- a nano-sized powder having a uniform size, phase and microstructure can be produced with reproducibility in a nano-sized controlled form.
- This powder can be applied to ceramic powder or metal and ceramic composite powder.
- Fig. 1 is a flow chart sequentially showing an example of steps in producing a nano-sized powder of the present invention.
- FIG. 2 is a schematic diagram of an ideal two-component nano-synthesis aggregate.
- FIG. 3 is a diagram showing thermogravimetric analysis (TG), differential thermal analysis (TDA), and temperature change of the container in a thermal explosion in the case of cyclotrimethylenetri-tolamine alone.
- FIG. 4 Schematic diagram of thermal detonation of single agglomerates of multi-component precursor agglomerates containing explosive components
- (A) is a multi-component precursor containing explosive components The state where the agglomerate is heated
- (B) shows the state immediately before the precursor agglomerate is thermally detonated
- (C) shows the nano-explosion state of the precursor agglomerate.
- FIG. 5 Thermogravimetric analysis (TG), differential thermal analysis (TDA) of thermal explosion of cyclotrimethylenetrinitramine and the temperature change of the container in the complex explosion synthesis of ceria-gadolinia solid solution in Example 1.
- TG Thermogravimetric analysis
- TDA differential thermal analysis
- FIG. 6 shows a transmission electron microscope (TEM) image of ceria-gadolinia powder obtained in Example 1.
- FIG. 7 XRD pattern of ceria-gadolinia nanopowder, where (a) shows the case of the ceria-gadolinia solid solution obtained in Example 1, and (b) shows the critical heating rate of Comparative Example 1 described later. It shows the case of ceria-gadolinia solid solution synthesized under the following conditions, that is, the normal combustion route.
- FIG. 8 shows a TEM image of cyclotrimethylene tri-tolamine particles synthesized alone in Example 4. It is a photograph.
- FIG. 9 Thermogravimetric analysis (TG), differential thermal analysis (TDA), and vessel temperature in thermal decomposition of ternary precursor agglomerates under the subcritical velocity conditions causing explosion in Comparative Example 1 It is a diagram showing a change.
- FIG. 10 is a diagram showing a TEM image of a ceria-gadolinia compound synthesized in Comparative Example 1.
- FIG. 11 is a transmission electron microscope image of the ceria-gadolinia powder obtained in Example 8.
- FIG. 12 is a schematic view of a two-component powder synthesized by a conventional wet chemistry method.
- the first method for producing a nanosize powder of the present invention comprises the first to third steps.
- the precursor agglomerates are saturated with explosive compounds when the single or multi-component precursor agglomerates are precipitated from a medium in which the raw material of the powder is dissolved. Or impregnating explosive compounds at the nano level to prepare precursor agglomerates containing explosive compounds.
- the precursor agglomerates containing explosive compounds are washed and dried while maintaining their component and morphological homogeneity.
- the precursor agglomerates containing explosive compounds that have been dried are A nano-sized powder composed of a single or multi-component is obtained by heating at a temperature rising rate sufficient to cause explosion in order to cause explosion.
- the explosive compound when the precursor agglomerate is first chemically precipitated from the powder raw material, the explosive compound is included, and the precursor agglomerate containing the explosive compound is added to the precursor agglomerate.
- nano-sized powder can be produced with good reproducibility by causing agglomeration due to a complex explosion due to the impact of high-energy explosion waves.
- a single or multi-component precursor agglomerate is chemically synthesized from a medium in which a powder raw material is melted.
- the precursor agglomerate containing the explosive compound is prepared by impregnating the precursor agglomerate and impregnating the precursor agglomerate with a nano-sized explosive compound prepared in advance.
- the subsequent second and third steps are the same as those in the first method for producing a nanosize powder of the present invention, and thus description thereof is omitted.
- a precursor agglomerate is first chemically precipitated from a powder raw material, and a nano-sized explosive compound prepared in advance is immersed in the precursor agglomerate.
- a precursor agglomerate containing this explosive compound By exploding a precursor agglomerate containing this explosive compound, the impact of a high-energy explosion wave causes agglomeration of the agglomeration due to a complex explosion, and the nano-sized powder is reproduced. It can be manufactured with good performance.
- nanoscale or nanosize particles are defined as particles having a diameter of about 1 to LOONm.
- the nano-sized powder can be a ceramic powder or a metal and ceramic composite powder. This ceramic powder can be single-component or multi-component.
- the nanosized powder may be heat treated. According to this heat treatment step, explosive products can be further removed from the obtained nano-sized powder, and the homogeneity of the powder composition and the improvement of the powder form can be achieved.
- FIG. 1 is a flow chart showing an example of steps in the case of producing the nano-sized powder of the present invention.
- step ST1 for example, a powder containing cyclotrimethylentri-tolamine particles as an explosive compound is prepared.
- This powder is ceramic powder, or
- Metal and ceramic composite powders can be used.
- the powder is first agglomerated into a precursor agglomerate.
- the precursor agglomerates are placed in a reaction vessel.
- the reactor is preheated.
- process ST5 Then, put the reaction vessel in the preheated reactor and heat the precursor agglomerates at ultra high speed.
- thermal detonation thermal explosion
- multiple nano-explosion at multiple locations spreads inside the precursor agglomerates.
- the explosive compound is cyclotrimethylene tri-tolamine
- the temperature of the thermal detonation is about 230 ° C.
- the thermal detonation initiation reaction begins in the nano-sized region, ie, hot spot. In this hot spot, the energy of the collision Z shock wave can be stored, converted into energy, and the reaction starts.
- FIG. 2 is a schematic diagram of an ideal two-component nano-synthesis aggregate.
- additive (dopant) component 2 is evenly distributed in substrate component 3.
- substrate component 3 In the production and use of nano-sized powders, the uniform distribution of components leads to a significant decrease in process temperature. Multi-component powders often result in heterogeneous multi-phase compounds having a non-uniform morphology that is more difficult to produce nano-sized powders.
- the explosive compound used in the method for producing a nano-sized powder by nano-explosive synthesis of the present invention is chemically unstable, that is, energetically unstable, and is called "explosion".
- explosion There is no particular limitation as long as the pressure changes rapidly, that is, a substance that causes expansion (hereinafter referred to as explosive as appropriate)! ,.
- Examples of such explosives include cyclotrimethylene tri-tolamine (C H N O), trimethyl
- TNT nitrotoluene
- nitroglycerin nitroglycerin
- glycerin nitroglycerin
- cyclotrimethylenetri-tolamine can be particularly preferably used.
- Cyclotrimethylenetri-tolamine is a widely used explosive compound, also known as RDX or hexogen. Hexamethylenetetramine (C H N) and concentrated nitric acid (HNO)
- FIG. 3 shows the thermogravimetric analysis of the thermal explosion with only cyclotrimethylenetri-tolamine (T (G), differential thermal analysis (TDA), and temperature change of the container.
- T (G) cyclotrimethylenetri-tolamine
- TDA differential thermal analysis
- the horizontal axis shows the elapsed time (seconds)
- the left vertical axis shows the thermogravimetric change (%) of TG
- the right vertical axis shows the TDA temperature difference ⁇ T (V) and the container temperature (° C). Speak.
- the heating rate is 10 ° CZ.
- the nano-sized powder material is saturated with explosive compounds from a medium in which the raw material of the nano-sized powder is melted, or explosive compounds.
- the process of precipitating single or multi-component precursor agglomerates soaked in the nano-level must be formed simultaneously during the decomposition of the metal nitrate with hexamethylenetetramine. Can do.
- nano-sized explosive compound prepared in advance used in the first step of the second production method of the present invention for example, a nano-sized cyclotrimethylene tri-toluene synthesized in advance is used. Mining particles can be used.
- the medium used in the present invention can be selected from those capable of dissolving the powder raw material, but a preferred medium is water.
- the powder raw material used in the present invention is selected from those that are soluble in the medium.
- a powder raw material a salt of a metal or a cation (hereinafter referred to as a cation as appropriate) can be used.
- a preferred medium is water.
- various lanthanoids such as cerium, gadolinium, and lanthanum, cobalt, nickel, manganese, zinc, norium, titanium, vanadium, niobium, tantalum
- examples include tungsten, molybdenum, magnesium, calcium, yttrium, zirconium, hafnium, aluminum, lead, copper, tin, scandium, indium, silicon, iron, strontium, and noble metal elements such as gold and platinum.
- anions that form salts with metals or cations are nitrate ions, hydrochloric acid ions, sulfate ions, oxalate ions, acetate ions, oxyhydroxide ions, hydroxide ions.
- erons anions that form salts with metals or cations
- metal nitrate When metal nitrate is used and hexamethylenetetraamine is used as a raw material for explosives (hereinafter referred to as an explosive source), a metal precursor-compound and a highly explosive explosive, cyclotrimethylenetri- Conveniently, tramin is produced at the same time.
- an explosive source a metal precursor-compound and a highly explosive explosive, cyclotrimethylenetri- Conveniently, tramin is produced at the same time.
- metal nitrates hydrated or anhydrous nitrate-oxides may be used.
- the starting cation source is a metal nitrate. It is not limited to. Chloride, oxalate, carbonate and the like are also useful for the preparation of precursor agglomerates. In this case, pre-synthesized nano-sized cyclotrimethylene tri-tolamine or other suitable explosive particles can be immersed in the precursor agglomerates taking advantage of colloidal technology.
- porous agglomerates Z agglomerates in which each component is homogeneously or relatively homogeneously (preliminary) distributed,
- Fine primary crystallites are obtained, and they do not cause solid agglomeration during the preliminary synthesis.
- hexamethylenetetraamine When hexamethylenetetraamine is used as an explosive source, the amount of hexamethylenetetramine and metal nitrate used may be appropriately changed depending on the composition of the nanopowder to be produced. Usually, 1 to 5 mol, preferably 1.5 to 5 mol, of hexamethylenetetramine is used in excess of 1 mol (mol) of metal nitrate (total amount in the case of multiple components). Hexa If methylenetetraamine is less than 1 mol, the metal nitrate will not be completely salted. Therefore, if it is less than 5 mol, the excess will only be removed by washing.
- hexamethylenetetramine is preferably used as a precipitant.
- hexamethylenetetraamine which serves as a precipitating agent, is usually used by separately dissolving it in a medium made of water, and the molar concentration at that time is about 0.001 to 5M.
- the precipitating agent in addition to hexamethylenetetramine, urea or hydroxyammonium can be used.
- hexamethylenetetraamine or urea is used.
- a precipitant such as hexamethylenetetraamine is added to coprecipitate a precursor agglomerate intermediate product that may be either crystalline or amorphous.
- the intermediate product of the precursor agglomerates may be both crystalline or amorphous.
- the stirring temperature may be any of a low temperature of about 0 to 20 ° C, a room temperature of about 20 to 25 ° C, and a high temperature of about 25 to 100 ° C.
- hot water treatment at 70 to 170 ° C, hot water precipitation or hot water coprecipitation can also be used.
- the multi-component suspension in a pre-synthesized aqueous salt solution that has just been dissolved diffuses with a precipitating agent such as hexamethylenetetraamine, Infused or sprayed.
- the precipitation time varies depending on the material used. 20 when precipitation is complete It may take a long time, for example 2 to 200 hours, at a temperature of ⁇ 85 ° C. However, in the case of ceria (dicerium cerium dioxide), precipitation is completed in a short time at 70 ° C.
- the second step in the production method of the present invention that is, the precursor mass infiltrated with the explosive compound is washed and dried while maintaining its component and morphological homogeneity.
- the precursor mass infiltrated with the explosive compound is washed and dried while maintaining its component and morphological homogeneity.
- the precursor powder When cyclotrimethylenetri-tolamine is used as the explosive, the precursor powder is prevented while cyclotrimethylenetri-tolamine is washed away, and during the washing and drying of precursor agglomerates such as multi-component systems. It is necessary to maintain the component and morphological homogeneity. For this reason, the produced precursor agglomerates may be repeatedly washed several times with an appropriate cleaning solution to remove residual acids such as HNO and other ionic impurities. As this cleaning solution,
- Ethanol can be used. Subsequently, the supernatant is centrifuged and washed until it becomes clear. Finally, the washing solution such as ethanol remaining at 60 ° C is slowly evaporated and removed by a dryer. At this time, in order to prevent ignition of explosive compounds during drying, there is a limit temperature in the drying process. This temperature is the ignition temperature of the explosive compound used. In the case of cyclotrimethylenetri-tolamine, the force ignition temperature depending on the average particle size is 170-180 ° C. Drying must be performed below this ignition temperature.
- Complex precursor agglomerates containing explosive compounds i.e. precursor agglomerates with explosive compounds
- precursor agglomerates with explosive compounds are agglomerated as they are without being agglomerated as well-dried powders or using a uniaxial press machine, etc. Put into a container.
- the above process is performed at the ignition temperature of the explosive compound.
- the precursor agglomerate with explosive compound needs to be rapidly raised from the combustion temperature of the explosive compound through its melting point to the temperature of its thermal detonation. Thermal detonation is highly dependent on the heating rate. For example, if the explosive is cyclotrimethylene tri-tolamine (CH -N-NO)
- a nano-sized single metal or multi-component metal oxide powder that is, a nano-sized ceramic powder having a homogeneous morphology and an accurate stoichiometric ratio, can be obtained in a very short time.
- a nano-sized single metal or multi-component metal oxide powder that is, a nano-sized ceramic powder having a homogeneous morphology and an accurate stoichiometric ratio, can be obtained in a very short time.
- ceramic nano-sized ceramic powder in which dopant oxide is dissolved in metal oxide powder can be synthesized.
- Sarako can also synthesize metal oxides modified with metals, ie, metal and ceramic composite powders.
- nanopowder containing primary crystallites having an average particle diameter of 2 to 15 nm can be produced.
- nano-aggregates with a particle size distribution of 20 to 80 nm can be produced from these nano-powders.
- FIG. 4 is a schematic diagram of thermal detonation of a single agglomerate among precursor agglomerates having a multi-component force containing explosive components.
- FIG. 4 (A) shows a state where the precursor agglomerate 10 composed of multiple components including explosive components is heated.
- the precursor agglomerate 10 composed of multiple components including explosive components is composed of the substrate component 3 and additive component 2 (see FIG. 2) of the two-component nanosynthetic aggregate 1 and the explosive fine particles 4. It has become.
- Fig. 4 (B) shows that a precursor agglomerate 10 composed of multiple components containing explosive components is thermally detonated. -Shows the state just before the moment.
- Fig. 4 (C) shows that the precursor agglomerate 10 composed of multiple components including explosive components is nano-explosed 12 and the resulting collection is accompanied by the formation of a nanoparticle solid solution 16 consisting of uniform aggregates. It shows the pulverized state due to agglomeration. As shown in the figure, nanoparticle solid solution 16 is generated in a finely divided state by nanoexplosion of two nanoparticle mixture 15.
- the cyclotrimethylene tri-tolamine nano-explosion begins in the nano-sized region, the so-called hot spot, which causes the accumulation of mechanical energy and conversion to chemical energy of the collision wave, and initiates the explosion reaction.
- the extremely fast heat Detoneshiyon (10- 8 sec / g) the beginning of each cyclotrimethylene tri - Toramin Number compressed to the same volume as the volume of particles thousand
- the instantaneous explosive force that is, the expansion of the compressed gas is 500 MW Zg, and the impact of the explosion wave that occurs subsequently shatters the surrounding objects, causing atomization and plastic deformation.
- a thermal baking or heat treatment step may be performed at a temperature higher than the explosion temperature, for example, 450 ° C. According to this thermal firing process, the obtained ceramic powder force can remove explosive products such as cyclotrimethylenetri-tolamine, improve the homogeneity of the powder composition and maintain the powder form. .
- Example 1 a nanosized powder of Ce Gdd ⁇ solid solution was produced. Nano powder synthesis
- cerium nitrate (hexahydrate) (Ce (NO) ⁇ 6 ⁇ 0, purity 99.9%)
- Linum (hexahydrate) (Gd (NO) ⁇ 6 ⁇ 0, purity: 9 ⁇ 9% and hexamethylenetetraami
- the total molar ratio of cerium nitrate + gadolinium nitrate is 1.0 mole. These materials are weighed so that the total concentration is 0.1 ImolZlOOOOcm 3 (ie, 0.1 M), and a stock solution that has a total strength of 250 cm 3 of nanopowder synthetic material is obtained by dissolving in distilled water. did.
- the amount of cerium and gadolinium and the amount of hexamethylenetetramine are Although it may be changed depending on the composition of the powder, the molar ratio is in the range of lZl. 5 to lZ5.
- hexamethylenetetraamine was separately used as a precipitant. Hexamethylenetetraamine was dissolved in purified water to a concentration of 1M to obtain a 150 cm 3 precipitant aqueous solution. The pH of this solution was 8.45 at 22 ° C o
- gadolinia precipitation with initial particle agglomeration occurs in less than 100-600 seconds at lower temperatures.
- gadolinia agglomerates are formed first.
- ceria nucleation, growth and agglomeration occur on the surface of the gadolinia agglomerates (see Figure 12).
- ternary precursor agglomerates are washed several times with ethanol (99.5%, reagent grade, manufactured by Kanto Yigaku) to remove residual nitric acid and other ionic impurities. It was. Continue centrifugation at lOOOOrpm for 5-60 minutes until the supernatant is clear Went.
- the ternary precursor agglomerates were washed, and finally the residual ethanol was slowly evaporated at 60 ° C using a dryer and dried.
- the washed three-component precursor agglomerates were redispersed in ethanol using an ultrasonic device (Shimadzu, USP-600 type) to form a suspension (slurry).
- This ultrasonic device is composed of a 20 kHz frequency and 160 W output oscillator and a probe using a titanium chip. The probe was inserted 30-50 mm below the surface of the suspension and treated for 30-600 seconds.
- the obtained ternary precursor agglomerate is a complex multicomponent precursor agglomerate composed of gadolinia-doped ceria particles containing cyclotrimethylenetri-tolamine.
- the particle size distribution of this ternary precursor agglomerate was measured using an analyzer (LSPZ-100, manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method (DLS) using laser light. The measurement was performed by dispersing a small amount of powder (5 mg or less) in distilled water.
- the measured particle size of the ternary precursor agglomerate was as wide as 37 to 630 nm. Such a wide particle size distribution is due to the fact that gadolinium and cerium oxide precipitate simultaneously.
- the composite powder agglomerates are taken from the combustion temperature of cyclotrimethylene tri-tolamine ( ⁇ 180 ° C.). Through its melting point ( ⁇ 204 ° C.) and rapidly rising to the temperature of its thermal detonation ( ⁇ 230 ° C.). Then, in a multi-component precursor agglomerate, a complex, multi-point nano explosion occurs, and nano-sized ceria and gadolinia force (hereinafter referred to as ceria-gadolinia powder as appropriate), That is, a ceramic powder in which gadolinia was dissolved in ceria was obtained. After this step, the obtained powder was further fired at a temperature of 450 ° C.
- FIG. 5 shows the thermogravimetric analysis (TG), differential thermal analysis (TDA), and thermal decomposition of cyclotrimethylenetri-tolamine in the complex explosion synthesis of ceria-gadolinia solid solution in Example 1. It is a figure which shows a temperature change. In the figure, the horizontal axis shows the elapsed time (minutes), and the left vertical The axis shows the thermogravimetric change (%) of TG, and the right vertical axis shows TDA temperature difference ( ⁇ TV) and container temperature (° C). As shown in the figure, the heating rate of the container is the result of 10 ° CZ. As is clear from FIG.
- FIG. 6 is a transmission electron microscope (TEM) image of the ceria-gadolinia powder obtained in Example 1.
- the TEM uses JEM-2000-FX manufactured by JEOL, with an acceleration voltage of 200 kV and a magnification of 30,000.
- ceria-gadolinia powder is a primary crystallite with an average particle size of l lnm, and the aggregate particle size distribution is 30-70nm, which is homogeneous and precise stoichiometric. Having a composition.
- Table 1 shows the particle sizes of the nano-sized powders obtained in Example 1 and Examples 2 to 7 described later.
- Example 7 La 2 0 3 27-485 9 to 54 8 to 57
- the phase of the obtained powder was identified using an X-ray diffractometer (manufactured by Rigaku, RINT2000 type). The measurement was performed at room temperature, and the X-ray diffraction (XRD) pattern was recorded by Ka lines generated by irradiating Cu with an electron beam of 40 kV 300 mA.
- XRD X-ray diffraction
- Figure 7 shows the XRD pattern of ceria-gadolinia nanopowder, where (a) is the ceria-gadolinia solid solution obtained in Example 1, and (b) is below the critical heating rate of Comparative Example 1 described below. That is, it shows a ceria-gadolinia solid solution synthesized by a normal combustion route.
- the horizontal axis represents the angle 20 (°)
- the vertical axis represents the X-ray diffraction intensity (arbitrary scale).
- Example 7 the nanopowder with ceria-gadolinia solid solution strength obtained in Example 1 has a composition of Ce Gd 2 O (see black circles ( ⁇ ) in the figure), and is almost equal to the stoichiometric amount.
- the XRD peak attributed to Ce Gd O is relatively broad, which is the same as in Example 1.
- Example 1 a powder having nano-sized ceria and gadolinia force, that is, a ceramic powder in which gadolinia is dissolved or doped in ceria.
- Example 2 As Example 2, a nanosized powder of Ce Gd O ⁇ solid solution was produced. Nano powder synthesis
- the molar ratio of the amount of cerium nitrate (hexahydrate): gadolinium chloride (hexahydrate): hexamethylenetetraamine 0.8: 0.2: 2.5.
- the sum of the molar ratios of cerium nitrate and gadolinium chloride is 1.
- Precipitation of gadolinia in an aqueous solution was carried out by spraying hexamethylentetraamine as a precipitating agent into an aqueous salt-gadolinium solution (hereinafter referred to as spraying as appropriate) before ceria synthesis.
- the temperature of the aqueous solution at this time was 3 ° C, and stirring was performed at lOOOrpm.
- the resulting powder consisted of agglomerated primary crystallites with a particle size of 3-4 nm. However, the redispersion of the powder has become effective due to the short ultrasonic treatment. In this step, a gadolinia concentrated suspension was obtained.
- an aqueous cerium nitrate solution was prepared.
- the gadolinia concentrated suspension and hexamethylenetetraamine solution in an aqueous cerium nitrate solution were heated at 70-90 ° C. and lOOOO rpm for 6 hours. For this reason, primary crystallites of 3 to 4 nm gadolinia gathered to form agglomerates of 4 to 340 nm, covered with synthesized ceria.
- the second step is carried out in the same manner as in Example 1, except that residual ammonium chloride ion (NH C1), residual nitric acid and other ionic impurities are removed from the ternary precursor agglomerates. , Dried
- the particle distribution of the complex multicomponent consisting of gadolinia-doped ceria with cyclotrimethylenetri-tolamine thus obtained, ie ternary precursor agglomerates, is 18-380 nm Met.
- the third step is carried out in the same manner as in Example 1, and the three-component precursor agglomerate is converted into its thermal detonation.
- the temperature rapidly increased to a temperature of Yong ( ⁇ 230 ° C), causing a nano explosion.
- non-isothermal firing was performed at a temperature of 450 ° C.
- gadolinia was dissolved in nano-sized ceria, that is, a Seria gadolinia powder was obtained.
- the average particle size of the primary crystallites is l lnm
- the particle size distribution of the aggregates is 20-70 nm
- Example 3 a nanosized powder of Ce Gdd ⁇ solid solution was produced. Nano powder used
- gadolinium precursor a hexahydrate gadolinium compound in aqueous solution
- stirring 1600 rpm before ceria (CeO) synthesis.
- a gadolinia suspension was obtained by spraying hexamethylenetetraamine into the aqueous solution.
- the amount of hexamethylenetetramine 2.5 (molar ratio) was used with respect to the salt gadolinium (hexahydrate) 1 (molar ratio).
- Salt gadolinium (hexahydrate) was dissolved in deionized water to bring the final cation source total concentration to 0.1M.
- the total amount of the solution containing hexamethylenetetraamine was 200 cm 3 .
- the aggregate was washed, and then the aggregate was dispersed in water to obtain a gadolinia dispersion.
- This gadolinia dispersion was mixed with an aqueous cerium nitrate (hexahydrate) solution at 1 ° C. and kept at 2 ° C. Mixing was performed in a cold bath temperature controlled at 2 ° C.
- the gadolinia concentrate suspension was added to the aqueous solution of cerium nitrate at 1600 rpm, followed by mixing with hexamethylenetetraamine by spraying and treating at 80-90 ° C for 6 hours to obtain a synthetic powder.
- the molar composition ratio between gadolinia and ceria was set to 0.2: 0.8 as in Example 1.
- This composite powder is composed of cerium and gadolinium with cyclotrimethylenetri-tolamine. It is a three-component precursor agglomerate consisting of humic compounds. Its particle size distribution is 13 to 175 nm.
- the ternary precursor agglomerate is subjected to a third step in the same manner as in Example 1 and rapidly raised to a temperature of thermal detonation ( ⁇ 230 ° C.).
- a nano-sized powder was synthesized by causing multiple nano explosions at multiple locations.
- the obtained nano-sized powder is a nano-sized ceria-gadolinia powder in which gadolinia is dissolved in nano-sized ceria.
- the particle size distribution of the ceria-gadolinia powder was 15 to 40 nm, and among the above Examples 1 to 3, the particle size was the smallest. In addition, there was no evidence of particle aggregation or growth during subsequent firing to 450 ° C (see Table 1).
- the particle size distribution after firing at 450 ° C slightly expanded from 15 to 40 nm force of the synthetic powder obtained by nano explosion to 12 to 55 nm.
- Example 4 a CeO nano-sized powder was produced.
- the starting material for nanopowder synthesis is
- Salty cerium (7 water salt) (CeCl ⁇ 7 ⁇ ⁇ ⁇ ⁇ ) as a ceria powder raw material, and Wako Pure as a precipitant
- ceria precipitation with cerium chloride aqueous solution with hexamethylenetetraamine as a precipitant was carried out by stirring at 70 ° C at lOOOrpm.
- the initial pH of 8.45 was measured with hexamethylenetetraamine solution at 22 ° C.
- the synthesis of cerium oxide was started at 22.degree. C. and stirred at a temperature of 70.degree. C. for 5 hours to precipitate 100% of ceria to obtain ceria aggregates.
- the particle size of the obtained ceria aggregate was 18 to 230 nm.
- the composition of each of the above materials and the solution was in accordance with Example 1.
- cyclotrimethylene tri-tolamine as an explosive was synthesized independently from concentrated nitric acid (90 to 95%) and hexamethylene tetraamine.
- 20 cm 3 of an aqueous solution containing 5 g of hexamethylenetetraamine as a solid is poured into 50 cm 3 of concentrated nitric acid stirred at 500 rpm and subjected to a reduction reaction at a temperature of 1 ° C. to form a cyclotrimethylene tri-tolamine suspension. did.
- FIG. 8 is a photograph showing a TEM image of cyclotrimethylene tri-tolamine particles synthesized alone in Example 4. The magnification is 100,000 times. As is clear from Fig. 8, the particle size is about 20-40nm. It can be seen that these are nano-sized particles having a relatively uniform particle size.
- cyclotrimethylene tri-tolamine was immersed in the ceria aggregate at a saturated or nano level.
- the immersion was performed by mixing the synthesized ceria aggregate with the synthesized cyclotrimethylene tri-tolamine suspension.
- the ceria aggregates were washed and redispersed in the same manner as in Example 1.
- a well-dried and redispersed ceria-powered two-component precursor agglomerate with cyclotrimethylene tri-tolamine is added to the thermal detonation of cyclotrimethylene tri-tolamine ( ⁇ 230 ° C.).
- a two-stage single process was applied in which the temperature was increased rapidly and then heated to 450 ° C and fired relatively slowly. This creates a complex and multi-site nano-explosion on the binary agglomerates.
- Example 4 a CeO nano-sized powder was obtained.
- the average particle size of this powder is 6 ⁇
- Example 5 a nano-sized powder of zirconia in which 3 mol% of yttria was dissolved was produced.
- the body was prepared by hot water precipitation from metal chloride and urea sol, washing and redispersion as follows.
- zirconium chloride oxide octahydrate
- ZrOCl ⁇ 8 ⁇ 0 purity 99%
- urea NH CONH, purity 99%
- Urea was mixed with the aqueous solution, and 200 cm 3 of a sol having an initial pH of 1.2 or 1.2 or less was homogenized by stirring and mixed, and then this sol was treated with hot water.
- the sol was filled in a fluororesin tetrahydride fluorocarbon container having a volume of 250 cm 3 to occupy 80% by volume, placed in a pressure vessel made of stainless steel, and the container was sealed.
- the sol, 1 Place in a dryer controlled to heat up to 50 ° C, perform hydrothermal treatment for 10 hours, wash and redisperse the hydrothermally precipitated agglomerates, and nanosize with 3 mol% yttria in solid solution Tetragonal zircon (hereinafter referred to as yttria-doped anhydrous zircoure as appropriate) powder was obtained.
- yttria-doped anhydrous zircoure Tetragonal zircon
- Example 5 nano-sized tetragonal zirconia powder in which 3 mol% of yttria was dissolved was obtained.
- the average particle size of this powder was about 30 nm (see Table 1).
- Example 6 a nano-sized powder was produced in which nano-sized platinum was contained in zircoure in which 3 mol% of yttria was dissolved.
- the preparation of 3 mol% yttria-stabilized zirconium powder and cyclotrimethylene tri-tolamine as an explosive were carried out in the same manner as in Example 5.
- nano-aggregates of yttria solid solution zircoure containing platinum of 1 to 7 nm were prepared as follows.
- Pt (II) ions Pt 2+
- This sonochemical reduction treatment involves a variable frequency Using a sound wave generator (Kaijo Co., Ltd. Model 4021), platinum nanoparticles were deposited in the pores of the agglomerate and on the surface thereof, and nano-aggregate of yttria solid-solution zircoa containing nano-sized platinum Got.
- Example 5 the nano-aggregated yttria solid solution zirconium nanoaggregate hecyclotrimethylene tri-tolamine containing nano-sized platinum was immersed, washed, redispersed, dried, and cyclohexane.
- a multi-component agglomerate (particle size: 3 to 265 nm) with yttria-doped anhydrous zircoure force with cyclotrimethylenetri-tolamine and yttria-doped anhydrous zircoure force with trimethylenetri-tolamine was obtained.
- This multi-component agglomerate was placed in a container as in Example 5 and rapidly raised to a temperature of heat detonation ( ⁇ 230 ° C.).
- Example 7 a nano-sized powder of lanthanum oxide (La 2 O 3) was produced.
- starting material La 2 O 3
- Xamethylenetetraamine was used. These reagents are manufactured by Wako Pure Chemical Industries. Concentrations and procedures were basically the same as in Example 1. The size of the lanthanum oxide nanopowder thus produced was about 9 to 54 nm (see Table 1).
- FIG. 9 shows thermogravimetric analysis (TG), differential thermal analysis (TDA), and thermal decomposition in the thermal decomposition of a ternary precursor agglomerate under sub-critical speed conditions causing explosion in Comparative Example 1.
- TG thermogravimetric analysis
- TDA differential thermal analysis
- FIG. 9 shows the temperature change of a container.
- the horizontal axis shows the passage of time (minutes)
- the left vertical axis shows the thermogravimetric change (%) of TG
- the right vertical axis shows the TDA temperature difference ⁇ TV) and container temperature (° C).
- the temperature rising rate of the container is 5 ° CZ.
- the subcritical temperature condition prevents complex heat detonation to the hot spot, and cyclotrimethylenetri-tolamine simply burns slowly, creating a combustion path, It can be seen that no nano-explosion has occurred.
- FIG. 10 shows a TEM image of the ceria-gadolinia compound synthesized in Comparative Example 1. As is clear from FIG. 10, it can be seen that high-density agglomerates composed of large, nonuniform, ultrafine primary crystallites, that is, gadolinia particles exist as black particles.
- Example 8 the same Ce Gd ⁇ solid solution nano-sized powder as in Examples 1-3 was produced.
- urea manufactured by Wako Pure Chemical Industries
- Urea was dissolved in deionized water to a concentration of 2% per 1- ⁇ salt and cerium and ⁇ salt and gadolinium.
- Shioi ⁇ cerium aqueous urea solution 200 cm 3 were prepared two samples with Shioi ⁇ gadolinium aqueous urea solution 100 cm 3. The total amount is 300cm 3 .
- the urea aqueous solution is sprayed into the salt cerium urea aqueous solution under a stirring condition of 1600 rpm. Formed the nucleus of ceria. The subsequent stirring at a predetermined temperature was 10 hours to prepare a ceria suspension.
- initial nucleation of the gadolinium complex was performed. The aqueous solution of sodium chloride gadolinium urea was sprayed into the ceria suspension synthesized above while stirring at 160 Orpm.
- Example 2 ceria and gadolinia were further added to ethanol (manufactured by Kanto Igaku, 99.5%) using an ultrasonic device (manufactured by Shimadzu, USP-600). Powerful agglomerates were redispersed.
- cyclotrimethylenetri-tolamine as an explosive was synthesized in the same manner as in Example 4 with concentrated nitric acid (manufactured by Wako Pure Chemicals, approximately 93%) and hexamethylenetetramine aqueous solution. Hexamethylenetetramine was dissolved in deionized water to a concentration of 0.1 M, and cyclotrimethylenetri-tolamine was produced and precipitated by adding it to concentrated nitric acid into this hexamethylenetetramine aqueous solution. As a result, an aqueous solution in which the nanoparticles of cyclotrimethylenetri-tolamine were well dispersed was obtained.
- the cyclotrimethylene tri-tolamine was immersed at a saturated or nano level in an agglomerate having ceria and gadolinia forces.
- the soaking was performed by mixing the agglomerates having ceria and gadolinia force with the synthesized cyclotrimethylene tri-tolamine suspension.
- a ternary precursor agglomerate consisting of ceria and gadolinium intermediate complex and cyclotrimethylenetri-tolamine was separated from the supernatant by centrifugation at lOOOOrpm for 15 minutes.
- T 70 ° C).
- FIG. 11 is a transmission electron microscope image of the ceria-gadolinia powder obtained in Example 8. The acceleration voltage is 200kV and the magnification is 15,000 times.
- Ceria is a primary crystallite with an average particle size of 6-14 nm doped with gadolinia, and the aggregate particle size distribution is 18-67 nm, with a homogeneous morphology and precise stoichiometric composition. !!
- the particle size of the powder after firing at 450 ° C. was 22 to 74 nm.
- Table 2 shows the particle sizes of the nano-sized powders obtained in Example 8 and Comparative Example 4 described later.
- Example 8 also in the synthesis method of Example 8, as in Examples 1 to 3, a powder composed of nano-sized ceria and gadolinia, that is, a ceramic powder in which gadolinia is dissolved or doped in ceria is obtained. Turned out to be.
- Example 4 a ceria-gadolinia compound was produced in the same manner as in Example 8, except that the temperature was raised to 450 ° C by a normal combustion process instead of the nano-explosion process of the third production process. It was. The temperature was raised to 5 ° CZ, and the temperature of the precursor agglomerates containing explosives was lower than the critical temperature rise rate causing explosion.
- the particle size of the precursor powder of Comparative Example 4 is 30 to 1260 nm, and particles of ceria-gadolinia (Ce Gd O) powder after the normal combustion process and firing at 450 ° C Diameter
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JP2007290959A (ja) * | 2006-04-25 | 2007-11-08 | Samsung Corning Co Ltd | 酸化イットリウム組成物、その製造方法及びそれを利用した酸化イットリウム層の製造方法 |
WO2009107681A1 (ja) * | 2008-02-25 | 2009-09-03 | 国立大学法人京都大学 | マイクロ波を用いた不純物ドープ金属酸化物の製造方法 |
JPWO2009107681A1 (ja) * | 2008-02-25 | 2011-08-04 | 国立大学法人京都大学 | マイクロ波を用いた不純物ドープ金属酸化物の製造方法 |
JP2011523928A (ja) * | 2008-05-27 | 2011-08-25 | イノブナノ−マテリアイス アバンサドス,ソシエダッド アノニマ | ナノメートルサイズのセラミック材料、その合成法及びその使用 |
JP2012505075A (ja) * | 2008-10-13 | 2012-03-01 | イノブナノ−マテリアイス アバンサドス,ソシエダッド アノニマ | ナノ粒子層で被覆されたセラミック粉末及びその調製方法 |
JP2014501601A (ja) * | 2010-10-15 | 2014-01-23 | イノブナノ−マテリアイス アバンサドス,ソシエダッド アノニマ | エマルジョンの調製及び爆発によるナノ物質の合成方法、そのナノ物質及びエマルジョン |
JP2014500785A (ja) * | 2010-10-18 | 2014-01-16 | イノブナノ−マテリアイス アバンサドス,ソシエダッド アノニマ | エマルジョンの乳化及び爆発が同時に行われるナノ物質の連続合成方法 |
CN104973615A (zh) * | 2015-06-26 | 2015-10-14 | 山东大学 | 一种纳米氧化钆粉体的微波燃烧制备方法 |
CN104985175A (zh) * | 2015-07-02 | 2015-10-21 | 广东光华科技股份有限公司 | 一种去除纳米金属粉体表面阴离子的方法 |
CN104985175B (zh) * | 2015-07-02 | 2017-03-08 | 广东光华科技股份有限公司 | 一种去除纳米金属粉体表面阴离子的方法 |
WO2021193968A1 (ja) * | 2020-03-27 | 2021-09-30 | 旭化成株式会社 | 粒子の製造方法及び粒子製造装置 |
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