WO2014041705A1 - 金属微粒子の製造方法 - Google Patents
金属微粒子の製造方法 Download PDFInfo
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- WO2014041705A1 WO2014041705A1 PCT/JP2012/075463 JP2012075463W WO2014041705A1 WO 2014041705 A1 WO2014041705 A1 WO 2014041705A1 JP 2012075463 W JP2012075463 W JP 2012075463W WO 2014041705 A1 WO2014041705 A1 WO 2014041705A1
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- fluid
- metal
- water
- fine particles
- polyol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
- B01F27/271—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
- B01F27/2712—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator provided with ribs, ridges or grooves on one surface
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1887—Stationary reactors having moving elements inside forming a thin film
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a method for producing metal fine particles.
- metal fine particles have been demanded in a wide range of fields such as catalysts, conductive materials, magnetic materials, secondary electron emission materials, light emitters, heat absorbers, energy storage materials, electrode materials, colorants, etc.
- Various metal fine particles having a particle size are required.
- the method for producing metal fine particles is roughly divided into a gas phase method and a liquid phase method.
- a gas phase method a method of thermally decomposing by spraying a solution containing metal ions in a high-temperature atmosphere is common, but not only it is difficult to obtain particles with a uniform particle size or crystallite size, There is a problem that the apparatus tends to be large and the energy cost is high, and the liquid phase method is currently the mainstream.
- Patent Document 1 in the case of a liquid phase method using substantially only water as a solvent, there is a problem that it is difficult to control the particle size and the formulation is complicated.
- a polyol reduction method using a polyhydric alcohol (polyol) as a solvent as described in Patent Document 2 or 3 has attracted attention from the viewpoint of improving the uniformity and dispersibility of the particle diameter.
- the polyol reduction method has problems such as requiring a reduction reaction for a long time at a high temperature and difficult to control the particle diameter in practice because a uniform reduction reaction is difficult.
- Patent Document 5 proposes a method of using a mixed solvent of a monohydric alcohol having 4 or less carbon atoms and a polyol, but it is constant in a state where a solvent having a monohydric alcohol having a low flash point is heated. Since the reaction is performed for a long time, not only is it difficult to control the reaction, but there is also a problem from the viewpoint of safety. From the above, there has been a demand for a method capable of producing uniform and homogeneous metal fine particles continuously and stably.
- the present applicant has provided a method for continuously and stably producing uniform and homogeneous metal fine particles as in Patent Document 6, but for a method of controlling the particle size of the obtained metal fine particles and the coefficient of variation thereof. It was not specifically disclosed.
- the solvent is not particularly limited as long as it can dissolve the metal compound, and examples thereof include water and organic solvents.
- the particle diameter of the metal fine particles obtained and the coefficient of variation thereof are controlled by controlling the ratio of water in the mixed solution of alcohol and alcohol.
- Patent Document 5 proposes a method using a mixed solution of a monovalent alcohol having 4 or less carbon atoms and a polyol and water, but the mixing ratio of the mixed solvent and water is controlled. Although it is described that the particle size of the deposited metal powder is controlled by doing so, there is no description that the coefficient of variation of the particle size of the deposited metal powder is controlled to less than 5%.
- the present invention provides a method for producing uniform and homogeneous metal fine particles continuously and stably more than ever, and controls the particle diameter and coefficient of variation of the obtained metal fine particles.
- An object of the present invention is to produce fine metal particles with controlled diameter and variation coefficient. More desirably, it is intended to provide a method for producing metal fine particles with improved productivity while controlling the particle diameter and coefficient of variation of the obtained metal fine particles.
- the present invention uses at least two kinds of fluids to be treated, and at least one kind of fluid to be treated contains at least one kind of metal and / or metal compound.
- a fluid, and at least one kind of fluid to be treated other than those described above is a fluid containing at least one kind of reducing agent, and the fluid to be treated is disposed to face the fluid.
- At least one of the fluid containing the metal compound and the fluid containing the at least one reducing agent is a water-containing polyol obtained by mixing water and a polyol.
- the present invention can be implemented as controlling the coefficient of variation to less than 5% by controlling the ratio of water contained in the water-containing polyol to a range of 5 wt% to 60 wt%.
- the present invention can be carried out as the polyol is at least one selected from ethylene glycol, propylene glycol, trimethylene glycol, tetraethylene glycol, polyethylene glycol, diethylene glycol, glycerin, and polypropylene glycol. .
- any one of the fluids containing the fluid containing the at least one metal and / or metal compound and the fluid containing the at least one reducing agent contains the water-containing polyol.
- the fluid containing the at least one metal and / or metal compound contains the water-containing polyol and contains the monohydric alcohol. It can be implemented as not.
- both of the fluids containing the fluid containing the at least one metal and / or metal compound and the fluid containing the at least one reducing agent contain the water-containing polyol, And it can implement as what does not contain monohydric alcohol.
- any one fluid to be treated of the fluid containing the at least one metal and / or metal compound and the fluid containing the at least one reducing agent forms the thin film fluid.
- it is provided with a separate introduction path that is independent of the flow path that passes between the two processing surfaces and through which one of the fluids to be processed flows, and at least one of the at least two processing surfaces Provided with at least one opening that leads to the separate introduction path, and either one of the fluid containing the at least one metal and / or metal compound and the fluid containing the at least one reducing agent.
- a processing fluid is introduced between the at least two processing surfaces through the opening, and the fluid containing the at least one metal and / or metal compound and the at least one reducing agent.
- a non-fluid may be implemented as being mixed in the thin film fluid.
- the metal and / or metal compound is at least one selected from nickel, silver, a nickel compound, and a silver compound
- the reducing agent is at least one selected from nickel and silver. It can be implemented as a reducing agent for precipitating seeds.
- the at least one metal compound is a nickel compound
- the at least one reducing agent is a reducing agent for depositing nickel
- an average value of particle diameters of the nickel fine particles to be deposited is It can be implemented as being 350 nm or less.
- a fluid pressure application mechanism which applies pressure to a fluid to be processed, and a first processing part provided with a first processing surface among the at least two processing surfaces. And a second processing part having a second processing surface among the at least two processing surfaces, and a rotation drive mechanism for relatively rotating these processing parts,
- the surface constitutes a part of a sealed flow path through which the fluid to be processed to which the pressure is applied flows, and at least a first of the first processing portion and the second processing portion.
- the processing portion includes a pressure receiving surface, and at least a part of the pressure receiving surface is constituted by the second processing surface, and the fluid pressure applying mechanism is formed on the pressure receiving surface by the fluid pressure applying mechanism.
- the second processing surface In response to the applied pressure, the second processing surface is moved away from the first processing surface.
- the above pressure is generated between the first processing surface and the second processing surface, which are arranged to face each other and are capable of approaching / separating at least one rotating relative to the other.
- the fluid to be treated forms the thin film fluid, and can be implemented as a method for producing metal fine particles in which metal fine particles are precipitated in the thin film fluid. .
- a fluid containing at least one kind of metal and / or metal compound and a fluid containing at least one kind of reducing agent are disposed opposite to each other, at least one of which can be approached and separated from the other.
- the ratio of water in the water-containing polyol does not contain a monohydric alcohol and contains a water-containing polyol in which water and a polyol are mixed in at least one of the fluids containing a reducing agent of a kind
- the ratio of water in the water-containing polyol is within the range of 5 wt% to 60 wt%.
- the production amount of metal fine particles per unit time can be increased by including a water-containing polyol in a fluid containing at least one metal and / or metal compound and increasing the ratio of water in the water-containing polyol.
- FIG. 1 is a schematic cross-sectional view of a fluid processing apparatus according to an embodiment of the present invention.
- (A) is a schematic plan view of a first processing surface of the fluid processing apparatus shown in FIG. 1, and (B) is an enlarged view of a main part of the processing surface of the apparatus.
- (A) is sectional drawing of the 2nd introducing
- (B) is the principal part enlarged view of the processing surface for demonstrating the 2nd introducing
- 3 is a SEM photograph of nickel fine particles produced in Sample 4.
- 3 is a TEM photograph of silver fine particles produced in Sample 11.
- 4 is a TEM photograph of silver particles produced in Sample 16.
- 7 is a graph showing changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (CV) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 1 to 7.
- 7 is a graph showing changes in the particle diameter (average value) of silver fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 8 to 16.
- 7 is a graph showing changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 18 to 24.
- FIG. 6 is a graph showing changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 25 to 30.
- 4 is a graph showing changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 32-36.
- Samples 37, 38, 35, and 39 show changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used in the second fluid.
- the metal in the present invention is not particularly limited. All metals on the chemical periodic table. Examples include metal elements such as Ti, Fe, W, Pt, Au, Cu, Ag, Pd, Ni, Mn, Co, Ru, V, Zn, Zr, Sn, In, Te, Ta, Bi, and Sb. It is done. These metals may be single-element metals, alloys containing multiple elements, or substances containing non-metallic elements in metal elements. Of course, it can also be implemented as an alloy of a base metal and a noble metal.
- the metal compound in the present invention is not particularly limited. Examples include metal salts, oxides, hydroxides, hydroxide oxides, nitrides, carbides, complexes, organic salts, organic complexes, organic compounds or their hydrates, organic solvates, and the like. .
- the metal salt is not particularly limited, but metal nitrates and nitrites, sulfates and sulfites, formates and acetates, phosphates and phosphites, hypophosphites and chlorides, oxy salts and Examples thereof include acetylacetonate salts or hydrates and organic solvates thereof. These metal compounds may be used alone or as a mixture.
- the reducing agent used in the present invention is a substance capable of reducing metals and / or metal compounds, preferably metal ions, and is not particularly limited, but is not limited to hydrazine or hydrazine monohydrate, sodium formaldehyde sulfoxylate, hydrogen Borohydride metal salt, aluminum hydride metal salt, triethylborohydride metal salt, glucose, citric acid, ascorbic acid, tannic acid, dimethylformamide, tetrabutylammonium borohydride, sodium hypophosphite (NaH 2 PO 2 ), Examples include metal compounds or ions thereof, preferably transition metal compounds or ions thereof (iron, titanium, etc.). Each of the above reducing agents may be used alone or as a mixture.
- a fluid containing at least one kind of metal and / or metal compound is used, and at least one kind of the above metal and / or metal compound is mixed with a solvent and dissolved or molecularly dispersed. It is preferable.
- a fluid containing at least one kind of reducing agent is used, and it is preferable to use at least one kind of reducing agent mixed with a solvent and dissolved or molecularly dispersed.
- At least one of the fluid containing at least one kind of metal and / or metal compound and the fluid containing at least one kind of reducing agent contains a water-containing polyol described later, and methanol or ethanol.
- a solvent used in a fluid containing at least one metal and / or metal compound and a solvent used in a fluid containing at least one reducing agent It is preferable to use the water-containing polyol for either solvent.
- the water-containing polyol used in the present invention is a mixture of water and a polyol. Although it does not specifically limit as water, Ion exchange water, RO water, pure water, ultrapure water, etc. are mentioned.
- the polyol is a dihydric or higher alcohol, and examples thereof include ethylene glycol, propylene glycol, trimethylene glycol, tetraethylene glycol, diethylene glycol, glycerin, polyethylene glycol, and polypropylene glycol.
- the particle diameter of the metal fine particles obtained and the coefficient of variation thereof can be adjusted according to the target metal species and the target particle size.
- the reducing power in the polyol reduction method generally depends on the temperature during reduction, the type of metal salt, the type of polyol, and the like.
- the particle diameter of the metal fine particles to be produced and the coefficient of variation thereof are controlled by controlling the reducing power according to the reduction temperature, the type of metal salt, the type of polyol, and the ratio of water contained in the water-containing polyol. Applicant believes that it can be controlled.
- the polyol reduction method includes a reduction of metal ions using a polyol and a separate reducing agent in addition to the reduction of metal ions by the polyol.
- the control of the particle size of the obtained metal fine particles is to increase the particle size by increasing the ratio of water in the water-containing polyol, and to reduce the ratio of water in the water-containing polyol. It is preferable to control the particle size to be small.
- the coefficient of variation of the particle diameter of the obtained metal fine particles is controlled by controlling the ratio of water in the water-containing polyol to a range of 5 wt% to 60 wt%, so that the coefficient of variation of the particle diameter is 5%. It is preferable to control to less than. And it is preferable to make a fluid containing at least one metal and / or metal compound by dissolving at least one metal and / or metal compound in a water-containing polyol.
- the solubility of a metal and / or metal compound is lower than when only water is used as a solvent.
- the concentration of the metal and / or metal compound in the fluid containing at least one metal and / or metal compound can be increased as compared with the case where only the polyol is used as the solvent.
- an apparatus capable of continuous production such as a fluid processing apparatus described later is used, the production amount and production efficiency can be dramatically improved.
- the ratio of water in the water-containing polyol is preferably controlled in the range of 5 wt% to 60 wt%, and more preferably in the range of 10 wt% to 55 wt%. It is possible to control the coefficient of variation of the particle diameter of the obtained metal fine particles to less than 5%. When the ratio of water in the water-containing polyol exceeds the range of 5 wt% to 60 wt%, the coefficient of variation of the particle diameter of the obtained metal fine particles becomes 5% or more.
- the applicant of the present application considers that the mixing ratio of water and polyol in the water-containing polyol and the reducing ability of the polyol influence the coefficient of variation of the particle diameter of the metal fine particles.
- the danger of the polyol as a flammable liquid can be reduced by mixing water, and when the ratio of water in the water-containing polyol exceeds 40 wt%, it can be excluded from the application of dangerous substances.
- Solvents other than the water-containing polyol used in the present invention are not particularly limited, and various solvents can be used. Solvents other than water-containing polyols are not particularly limited, but water and polyols used in the water-containing polyols described above, alcohol-based organic solvents such as methanol and ethanol, ketone-based organic solvents such as acetone and methyl ethyl ketone, ethyl acetate And ester organic solvents such as butyl acetate, ether organic solvents such as dimethyl ether and dibutyl ether, aromatic organic solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon organic solvents such as hexane and pentane.
- alcohol-based organic solvents such as methanol and ethanol
- ketone-based organic solvents such as acetone and methyl ethyl ketone
- ester organic solvents such as butyl acetate
- solvents other than a water containing polyol can be mentioned. Moreover, you may use the acidic substance mentioned later as solvents other than a water containing polyol. Each of the above solvents may be used alone or in combination. In the present invention, water and a solvent other than the polyol may or may not be used to the extent that does not affect the present invention.
- solvents other than water and polyol include ketone organic solvents such as acetone and methyl ethyl ketone, ester organic solvents such as ethyl acetate and butyl acetate, ether organic solvents such as dimethyl ether and dibutyl ether, benzene, toluene, and xylene. And aromatic hydrocarbon organic solvents such as hexane and pentane.
- each of the above solvents may be used alone or in combination.
- the above alcohol-based organic solvent or polyol is used as a solvent, there is an advantage that the solvent itself works as a reducing agent.
- the fluid to be treated does not contain a monohydric alcohol.
- a basic substance or an acidic substance may be mixed or dissolved in a water-containing polyol or a solvent other than the water-containing polyol.
- Examples of basic substances include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium isopropoxide, and amine compounds such as triethylamine, 2-diethylaminoethanol and diethylamine. Can be mentioned.
- acidic substances include inorganic acids such as aqua regia, hydrochloric acid, nitric acid, fuming nitric acid, sulfuric acid and fuming sulfuric acid, and organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid and trichloroacetic acid. It is done.
- inorganic acids such as aqua regia, hydrochloric acid, nitric acid, fuming nitric acid, sulfuric acid and fuming sulfuric acid
- organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid and trichloroacetic acid. It is done.
- a fluid containing at least one kind of metal and / or metal compound and a fluid containing at least one kind of reducing agent are disposed so as to be able to approach and separate from each other, and at least one of them is the other. It is preferable to use a method of mixing in a thin film fluid between the processing surfaces rotating with respect to the surface.
- the metal can be mixed by using a device having the same principle as the device shown in Patent Document 6. It is preferable to deposit fine particles.
- the fluid processing apparatus shown in FIGS. 1 to 3 processes an object to be processed between processing surfaces in a processing unit in which at least one of approaching and separating can rotate relative to the other,
- the first fluid which is the first fluid to be treated
- the second fluid which is the second fluid to be treated, of the fluids to be treated is introduced between the processing surfaces from another flow path provided with the first fluid and the second fluid between the processing surfaces.
- U indicates the upper side
- S indicates the lower side.
- the upper, lower, front, rear, left and right only indicate a relative positional relationship, and do not specify an absolute position.
- R indicates the direction of rotation.
- C indicates the centrifugal force direction (radial direction).
- This apparatus uses at least two kinds of fluids as a fluid to be treated, and at least one kind of fluid includes at least one kind of an object to be treated and is opposed to each other so as to be able to approach and separate.
- a processing surface at least one of which rotates with respect to the other, and the above-mentioned fluids are merged between these processing surfaces to form a thin film fluid.
- An apparatus for processing an object to be processed As described above, this apparatus can process a plurality of fluids to be processed, but can also process a single fluid to be processed.
- This fluid processing apparatus includes first and second processing units 10 and 20 that face each other, and at least one of the processing units rotates.
- the opposing surfaces of both processing parts 10 and 20 are processing surfaces.
- the first processing unit 10 includes a first processing surface 1
- the second processing unit 20 includes a second processing surface 2.
- Both the processing surfaces 1 and 2 are connected to the flow path of the fluid to be processed and constitute a part of the flow path of the fluid to be processed.
- the distance between the processing surfaces 1 and 2 can be changed as appropriate, but is usually adjusted to 1 mm or less, for example, a minute distance of about 0.1 ⁇ m to 50 ⁇ m.
- the fluid to be processed that passes between the processing surfaces 1 and 2 becomes a forced thin film fluid forced by the processing surfaces 1 and 2.
- the apparatus When a plurality of fluids to be processed are processed using this apparatus, the apparatus is connected to the flow path of the first fluid to be processed and forms a part of the flow path of the first fluid to be processed. At the same time, a part of the flow path of the second fluid to be treated is formed separately from the first fluid to be treated. And this apparatus performs processing of fluid, such as making both flow paths merge and mixing both the to-be-processed fluids between the processing surfaces 1 and 2, and making it react.
- “treatment” is not limited to a form in which the object to be treated reacts, but also includes a form in which only mixing and dispersion are performed without any reaction.
- the first holder 11 that holds the first processing portion 10 the second holder 21 that holds the second processing portion 20, a contact pressure applying mechanism, a rotation drive mechanism, A first introduction part d1, a second introduction part d2, and a fluid pressure imparting mechanism p are provided.
- the first processing portion 10 is an annular body, more specifically, a ring-shaped disk.
- the second processing unit 20 is also a ring-shaped disk.
- the materials of the first and second processing parts 10 and 20 are metal, carbon, ceramic, sintered metal, wear-resistant steel, sapphire, other metals subjected to hardening treatment, hard material lining, Those with coating, plating, etc. can be used.
- at least a part of the first and second processing surfaces 1 and 2 facing each other is mirror-polished in the processing units 10 and 20.
- the surface roughness of this mirror polishing is not particularly limited, but is preferably Ra 0.01 to 1.0 ⁇ m, more preferably Ra 0.03 to 0.3 ⁇ m.
- At least one of the holders can be rotated relative to the other holder by a rotational drive mechanism (not shown) such as an electric motor.
- Reference numeral 50 in FIG. 1 denotes a rotation shaft of the rotation drive mechanism.
- the first holder 11 attached to the rotation shaft 50 rotates and is used for the first processing supported by the first holder 11.
- the unit 10 rotates with respect to the second processing unit 20.
- the second processing unit 20 may be rotated, or both may be rotated.
- the first and second holders 11 and 21 are fixed, and the first and second processing parts 10 and 20 are rotated with respect to the first and second holders 11 and 21. May be.
- At least one of the first processing unit 10 and the second processing unit 20 can be approached / separated from at least either one, and both processing surfaces 1 and 2 can be approached / separated. .
- the second processing unit 20 approaches and separates from the first processing unit 10, and the second processing unit 20 is disposed in the storage unit 41 provided in the second holder 21. It is housed in a hauntable manner.
- the first processing unit 10 may approach or separate from the second processing unit 20, and both the processing units 10 and 20 may approach or separate from each other. It may be a thing.
- the accommodating portion 41 is a recess that mainly accommodates a portion of the second processing portion 20 on the side opposite to the processing surface 2 side, and is a groove that has a circular shape, that is, is formed in an annular shape in plan view. .
- the accommodating portion 41 accommodates the second processing portion 20 with a sufficient clearance that allows the second processing portion 20 to rotate.
- the second processing unit 20 may be arranged so that only the parallel movement is possible in the axial direction, but by increasing the clearance, the second processing unit 20 is
- the center line of the processing part 20 may be tilted and displaced so as to break the relationship parallel to the axial direction of the storage part 41. Furthermore, the center line of the second processing part 20 and the storage part 41 may be displaced.
- the center line may be displaced so as to deviate in the radial direction. As described above, it is desirable to hold the second processing unit 20 by the floating mechanism that holds the three-dimensionally displaceably.
- the above-described fluid to be treated is subjected to both treatment surfaces from the first introduction part d1 and the second introduction part d2 in a state where pressure is applied by a fluid pressure application mechanism p configured by various pumps, potential energy, and the like. It is introduced between 1 and 2.
- the first introduction part d1 is a passage provided in the center of the annular second holder 21, and one end of the first introduction part d1 is formed on both processing surfaces from the inside of the annular processing parts 10, 20. It is introduced between 1 and 2.
- the second introduction part d2 supplies the second processing fluid to be reacted with the first processing fluid to the processing surfaces 1 and 2.
- the second introduction part d ⁇ b> 2 is a passage provided inside the second processing part 20, and one end thereof opens at the second processing surface 2.
- the first fluid to be processed that has been pressurized by the fluid pressure imparting mechanism p is introduced from the first introduction part d1 into the space inside the processing parts 10 and 20, and the first processing surface 1 and the second processing surface 2 are supplied. It passes between the processing surfaces 2 and tries to pass outside the processing portions 10 and 20. Between these processing surfaces 1 and 2, the second fluid to be treated pressurized by the fluid pressure applying mechanism p is supplied from the second introduction part d 2, merged with the first fluid to be treated, and mixed.
- the above-mentioned contact surface pressure applying mechanism applies a force that acts in a direction in which the first processing surface 1 and the second processing surface 2 approach each other to the processing portion.
- the contact pressure applying mechanism is provided in the second holder 21 and biases the second processing portion 20 toward the first processing portion 10.
- the contact surface pressure applying mechanism is a force that pushes in a direction in which the first processing surface 1 of the first processing unit 10 and the second processing surface 2 of the second processing unit 20 approach (hereinafter referred to as contact pressure). It is a mechanism for generating.
- a thin film fluid having a minute film thickness of nm to ⁇ m is generated by the balance between the contact pressure and the force for separating the processing surfaces 1 and 2 such as fluid pressure. In other words, the distance between the processing surfaces 1 and 2 is kept at a predetermined minute distance by the balance of the forces.
- the contact surface pressure applying mechanism is arranged between the accommodating portion 41 and the second processing portion 20.
- a spring 43 that biases the second processing portion 20 in a direction approaching the first processing portion 10 and a biasing fluid introduction portion 44 that introduces a biasing fluid such as air or oil.
- the contact surface pressure is applied by the spring 43 and the fluid pressure of the biasing fluid. Any one of the spring 43 and the fluid pressure of the urging fluid may be applied, and other force such as magnetic force or gravity may be used.
- the second processing unit 20 causes the first treatment by the separation force generated by the pressure or viscosity of the fluid to be treated which is pressurized by the fluid pressure imparting mechanism p against the bias of the contact surface pressure imparting mechanism.
- the first processing surface 1 and the second processing surface 2 are set with an accuracy of ⁇ m by the balance between the contact surface pressure and the separation force, and a minute amount between the processing surfaces 1 and 2 is set. An interval is set.
- the separation force includes the fluid pressure and viscosity of the fluid to be processed, the centrifugal force due to the rotation of the processing part, the negative pressure when the urging fluid introduction part 44 is negatively applied, and the spring 43 is pulled.
- the force of the spring when it is used as a spring can be mentioned.
- This contact surface pressure imparting mechanism may be provided not in the second processing unit 20 but in the first processing unit 10 or in both.
- the second processing unit 20 has the second processing surface 2 and the inside of the second processing surface 2 (that is, the first processing surface 1 and the second processing surface 2).
- a separation adjusting surface 23 is provided adjacent to the second processing surface 2 and located on the entrance side of the fluid to be processed between the processing surface 2 and the processing surface 2.
- the separation adjusting surface 23 is implemented as an inclined surface, but may be a horizontal surface.
- the pressure of the fluid to be processed acts on the separation adjusting surface 23 to generate a force in a direction in which the second processing unit 20 is separated from the first processing unit 10. Accordingly, the pressure receiving surfaces for generating the separation force are the second processing surface 2 and the separation adjusting surface 23.
- the proximity adjustment surface 24 is formed on the second processing portion 20.
- the proximity adjustment surface 24 is a surface opposite to the separation adjustment surface 23 in the axial direction (upper surface in FIG. 1), and the pressure of the fluid to be processed acts on the second processing portion 20. A force is generated in a direction that causes the first processing unit 10 to approach the first processing unit 10.
- the pressure of the fluid to be processed that acts on the second processing surface 2 and the separation adjusting surface 23, that is, the fluid pressure, is understood as a force constituting an opening force in the mechanical seal.
- the projected area A1 of the proximity adjustment surface 24 projected on a virtual plane orthogonal to the approaching / separating direction of the processing surfaces 1 and 2, that is, the protruding and protruding direction (axial direction in FIG. 1) of the second processing unit 20 The area ratio A1 / A2 of the total area A2 of the projected areas of the second processing surface 2 and the separation adjusting surface 23 of the second processing unit 20 projected onto the virtual plane is called a balance ratio K. This is important for the adjustment of the opening force.
- the opening force can be adjusted by the pressure of the fluid to be processed, that is, the fluid pressure, by changing the balance line, that is, the area A1 of the adjustment surface 24 for proximity.
- P1 represents the pressure of the fluid to be treated, that is, the fluid pressure
- K represents the balance ratio
- k represents the opening force coefficient
- Ps represents the spring and back pressure
- the proximity adjustment surface 24 may be implemented with a larger area than the separation adjustment surface 23.
- the fluid to be processed becomes a thin film fluid forced by the two processing surfaces 1 and 2 holding the minute gaps, and tends to move to the outside of the annular processing surfaces 1 and 2.
- the mixed fluid to be processed does not move linearly from the inside to the outside of the two processing surfaces 1 and 2, but instead has an annular radius.
- a combined vector of the movement vector in the direction and the movement vector in the circumferential direction acts on the fluid to be processed and moves in a substantially spiral shape from the inside to the outside.
- the rotating shaft 50 is not limited to a vertically arranged shaft, and may be arranged in the horizontal direction, or may be arranged in an inclined manner. This is because the fluid to be processed is processed at a fine interval between the processing surfaces 1 and 2 and the influence of gravity can be substantially eliminated. Further, this contact surface pressure applying mechanism also functions as a buffer mechanism for fine vibration and rotational alignment when used in combination with a floating mechanism that holds the second processing portion 20 in a displaceable manner.
- ⁇ ⁇ / ⁇ is the kinematic viscosity
- V the representative speed
- L the representative length
- ⁇ the density
- ⁇ the viscosity.
- the fluid flow has a critical Reynolds number as a boundary, laminar flow below the critical Reynolds number, and turbulent flow above the critical Reynolds number. Since the space between the processing surfaces 1 and 2 of the fluid processing apparatus is adjusted to a minute distance, the amount of fluid held between the processing surfaces 1 and 2 is extremely small.
- a acceleration
- m mass
- v velocity
- R represents a radius
- At least one of the first and second processing parts 10 and 20 may be cooled or heated to adjust the temperature.
- the first and second processing parts 10 and 10 are adjusted.
- 20 are provided with temperature control mechanisms (temperature control mechanisms) J1, J2.
- the temperature of the introduced fluid to be treated may be adjusted by cooling or heating. These temperatures can also be used for the deposition of the treated material, and also to generate Benard convection or Marangoni convection in the fluid to be treated between the first and second processing surfaces 1 and 2. May be set.
- a groove-like recess 13 extending from the center side of the first processing portion 10 to the outside, that is, in the radial direction is formed on the first processing surface 1 of the first processing portion 10. May be implemented.
- the planar shape of the recess 13 is curved or spirally extending on the first processing surface 1, or is not shown, but extends straight outward, L It may be bent or curved into a letter shape or the like, continuous, intermittent, or branched.
- the recess 13 can be implemented as one formed on the second processing surface 2, and can also be implemented as one formed on both the first and second processing surfaces 1, 2.
- the base end of the recess 13 reaches the inner periphery of the first processing unit 10.
- the tip of the recess 13 extends toward the outer peripheral surface of the first processing surface 1, and its depth (cross-sectional area) gradually decreases from the base end toward the tip.
- a flat surface 16 without the recess 13 is provided between the tip of the recess 13 and the outer peripheral surface of the first processing surface 1.
- the opening d20 of the second introduction part d2 is provided in the second processing surface 2, it is preferably provided at a position facing the flat surface 16 of the facing first processing surface 1.
- the opening d20 is desirably provided on the downstream side (outside in this example) from the concave portion 13 of the first processing surface 1.
- it is installed at a position facing the flat surface 16 on the outer diameter side from the point where the flow direction when introduced by the micropump effect is converted into a laminar flow direction in a spiral shape formed between the processing surfaces. It is desirable to do.
- the distance n in the radial direction from the outermost position of the recess 13 provided in the first processing surface 1 is preferably about 0.5 mm or more.
- the shape of the opening d20 may be circular as shown by a solid line in FIG. 2B or FIG. 3B, or may be a ring-shaped disc as shown by a dotted line in FIG. 2B.
- a concentric ring shape surrounding the central opening of the working surface 2 may be used.
- the annular opening d20 may not be provided concentrically around the central opening of the processing surface 2. Further, when the opening has an annular shape, the annular opening may be continuous or discontinuous.
- the second fluid introduced between the processing surfaces 1 and 2 can be introduced under the same condition, Fluid processing such as uniform diffusion, reaction, and precipitation can be performed. When mass-producing fine particles, it is preferable that the opening has an annular shape.
- the second introduction part d2 can have directionality.
- the introduction direction from the opening d20 of the second processing surface 2 is inclined with respect to the second processing surface 2 at a predetermined elevation angle ( ⁇ 1).
- the elevation angle ( ⁇ 1) is set to be more than 0 degrees and less than 90 degrees, and in the case of a reaction with a higher reaction rate, it is preferably set at 1 to 45 degrees.
- the introduction direction from the opening d ⁇ b> 20 of the second processing surface 2 has directionality in the plane along the second processing surface 2.
- the introduction direction of the second fluid is a component in the radial direction of the processing surface that is an outward direction away from the center and a component with respect to the rotation direction of the fluid between the rotating processing surfaces. Is forward.
- a line segment in the radial direction passing through the opening d20 and extending outward is defined as a reference line g and has a predetermined angle ( ⁇ 2) from the reference line g to the rotation direction R. This angle ( ⁇ 2) is also preferably set to more than 0 degree and less than 90 degrees.
- This angle ( ⁇ 2) can be changed and implemented in accordance with various conditions such as the type of fluid, reaction speed, viscosity, and rotational speed of the processing surface.
- the second introduction part d2 may not have any directionality.
- the number of fluids to be treated and the number of flow paths are two, but may be one, or may be three or more.
- the second fluid is introduced between the processing surfaces 1 and 2 from the second introduction part d2, but this introduction part may be provided in the first processing part 10 or provided in both. Good. Moreover, you may prepare several introduction parts with respect to one type of to-be-processed fluid.
- the shape, size, and number of the opening for introduction provided in each processing portion are not particularly limited, and can be appropriately changed. Further, an opening for introduction may be provided immediately before or between the first and second processing surfaces 1 and 2 or further upstream.
- the second fluid is introduced from the first introduction part d1 and the first fluid is introduced from the second introduction part d2 contrary to the above. May be introduced.
- the expressions “first” and “second” in each fluid have only an implication for identification that they are the nth of a plurality of fluids, and a third or higher fluid may exist.
- processes such as precipitation / precipitation or crystallization are arranged so as to face each other so as to be able to approach / separate, and at least one rotates for the other. Occurs with uniform mixing between surfaces 1 and 2 forcibly.
- the particle size and monodispersity of the processed material to be processed are the rotational speed and flow velocity of the processing parts 10 and 20, the distance between the processing surfaces 1 and 2, the raw material concentration of the processed fluid, or the processed fluid. It can be controlled by appropriately adjusting the solvent species and the like.
- a fluid containing one type of metal and / or metal compound and a fluid containing at least one type of reducing agent are mixed to deposit metal fine particles.
- at least one of the fluid containing at least one metal and / or metal compound and the fluid containing at least one reducing agent contains a water-containing polyol and is monovalent. It contains no alcohol and controls the ratio of water contained in the water-containing polyol.
- the metal fine particles are deposited in the thin film fluid between the processing surfaces 1 and 2 of the apparatus shown in FIG. This happens with forced uniform mixing.
- a fluid containing at least one kind of metal and / or metal compound as a first fluid is disposed opposite to each other so as to be able to approach and separate from the first introduction part d1 which is one flow path, and at least one of them is disposed. It introduce
- a fluid containing at least one kind of reducing agent as a second fluid is directly introduced into the first fluid film formed between the processing surfaces 1 and 2 from the second introduction part d2 which is a separate flow path.
- the first fluid and the second fluid are disposed between the processing surfaces 1 and 2 whose distance is fixed by the pressure balance between the supply pressure of the fluid to be processed and the pressure applied between the rotating processing surfaces.
- the metal fine particles can be deposited.
- the fluid containing at least one kind of metal and / or metal compound as the first fluid contains one kind of metal element, single metal fine particles can be deposited, and 2 By including more than one kind of metal element, alloy particles of these metal elements can be precipitated.
- the second fluid is introduced from the first introduction part d 1 and the first fluid is introduced from the second introduction part d 2. It may be introduced.
- the expressions “first” and “second” in each fluid have only an implication for identification that they are the nth of a plurality of fluids, and a third or higher fluid may exist.
- the third introduction part d3 can be provided in the processing apparatus.
- a fluid containing at least one metal and / or metal compound, a fluid containing at least one metal and / or metal compound different from the metal and / or metal compound used in the first fluid as the second fluid third It is possible to introduce each of the fluids containing at least one reducing agent as the fluid separately into the processing apparatus. If it does so, the density
- the fourth or more introduction portions are provided, and the fluid to be introduced into the processing apparatus can be subdivided in this way.
- the temperature of the fluid to be processed such as the first and second fluids is controlled, and the temperature difference between the first fluid and the second fluid (that is, the temperature difference between the supplied fluids to be processed) is controlled.
- the temperature of each processed fluid is measured. It is also possible to add a mechanism for heating or cooling each fluid to be processed introduced between the processing surfaces 1 and 2.
- the pH of a fluid containing at least one metal and / or metal compound or a fluid containing at least one reducing agent is not particularly limited. It can be appropriately changed depending on the type and concentration of the metal and / or metal compound or reducing agent used, the purpose, the target metal species, and the like.
- Dispersants and surfactants can be used according to the purpose and necessity. Although it does not specifically limit, As a surfactant and a dispersing agent, various commercially available products generally used, products, or newly synthesized products can be used. Although it does not specifically limit, Dispersants, such as anionic surfactant, a cationic surfactant, a nonionic surfactant, various polymers, etc. can be mentioned. These may be used alone or in combination of two or more. Further, when polyethylene glycol, polypropylene glycol or the like is used as a polyol, the polyol also acts as a dispersant.
- the temperature at which the fluid containing at least one metal and / or metal compound and the fluid containing at least one reducing agent are mixed is not particularly limited. It can be carried out at an appropriate temperature depending on the type of metal and / or metal compound to be used, the type of reducing agent, the target metal species, the pH of each fluid, and the like.
- the metal fine particles in the present invention can be implemented even if they partially contain oxides, hydroxides, oxide hydroxides, and the like.
- “from the center” means “from the first introduction part d1” of the processing apparatus shown in FIG. 1, and the first fluid is introduced from the first introduction part d1.
- the first fluid to be treated refers to the second fluid to be treated, which is introduced from the second introduction part d2 of the treatment apparatus shown in FIG.
- the opening d20 of the second introduction part d2 a concentric annular shape surrounding the central opening of the processing surface 2 was used as shown by a dotted line in FIG.
- X-ray diffraction measurement For the X-ray diffraction (XRD) measurement, a powder X-ray diffraction measurement apparatus X'Pert PRO MPD (manufactured by XRD Spectris PANalytical Division) was used. The measurement conditions are a Cu cathode, a tube voltage of 45 kV, a tube current of 40 mA, 0.016 step / 10 sec, and a measurement range of 10 to 100 [° 2 Theta] (Cu). The crystallite size of the obtained dry powder of nickel fine particles was calculated from the XRD measurement results. For the silicon polycrystalline disc, a peak confirmed at 47.3 ° C.
- a fluid containing a nickel compound and a fluid containing a reducing agent are disposed to face each other and have a treatment surface that can be approached and separated. Then, at least one was mixed in a thin film fluid formed between the processing surfaces 1 and 2 rotating with respect to the other to produce nickel fine particles as metal fine particles in the thin film fluid.
- a fluid containing a nickel compound as a first fluid is introduced between the processing surfaces 1 and 2 as a second fluid while feeding a fluid containing a nickel compound at a supply pressure of 0.50 MPaG and a rotation speed of 1700 rpm. Then, the first fluid and the second fluid were mixed in the thin film fluid.
- a nickel fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged nickel fine particle dispersion is placed on a magnet, the nickel fine particles are allowed to settle, the supernatant liquid is removed, and then washing with pure water is performed three times. The resulting wet cake is subjected to atmospheric pressure at 25 ° C. To dry powder of nickel fine particles.
- Table 1 shows the ratio of water in the water-containing polyol used for the first fluid
- Table 2 shows the average value of the particle diameters of the nickel fine particles obtained (in Table 2, “denoted as particle diameter”) and the particle diameter. Coefficient of variation (C.V.) and crystallite diameter.
- the temperature of the first fluid and the second fluid is adjusted to a temperature immediately before introducing each of the first fluid and the second fluid into the processing apparatus (more specifically, immediately before introducing between the processing surfaces 1 and 2). This is the temperature measured by heating and cooling.
- NiSO 4 ⁇ 6H 2 O is nickel sulfate hexahydrate
- EG is ethylene glycol
- PEG 600 polyethylene glycol 600
- PW is pure water
- HMH is hydrazine monohydrate
- KOH Indicates potassium hydroxide.
- FIG. 7 shows changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 1 to 7. Show.
- the particle diameter of nickel fine particles, the coefficient of variation thereof, and the crystallite diameter can be controlled.
- the particle size and crystallite size of the nickel fine particles can be controlled to be increased by increasing the ratio of water in the water-containing polyol, and the nickel fine particles can be controlled by decreasing the ratio of water in the water-containing polyol. It was confirmed that the particle size and crystallite size can be controlled to be small. It was also confirmed that the coefficient of variation of the particle diameter of the nickel fine particles was less than 5% by controlling the ratio of water in the water-containing polyol to a range of 5 wt% to 60 wt%.
- the ratio of water in the water-containing polyol contained in the first fluid is increased, a reduction reaction can be performed under a condition in which the temperature of the first fluid is low, and as a result, the reaction temperature when depositing nickel fine particles is lowered. Therefore, it was confirmed that nickel fine particles can be produced at low cost and low energy as compared with the conventional manufacturing method.
- the first fluid of Sample 1 using a polyol that does not contain water as a solvent a precipitate is formed after 30 minutes from the preparation of the first fluid at room temperature (25 ° C.). Even when the fluid was heated, the precipitate did not dissolve. Therefore, it was determined that the first fluid of Sample 1 was inappropriate as a fluid used for producing nickel fine particles.
- a fluid containing a silver compound and a fluid containing a reducing agent are disposed to face each other and can be approached and separated.
- Silver fine particles were produced as metal fine particles in the thin film fluid by mixing in a thin film fluid formed between the processing surfaces 1 and 2 having at least one surface rotated with respect to the other.
- a fluid containing a silver compound as a first fluid is introduced between the processing surfaces 1 and 2 as a second fluid while feeding a fluid containing a silver compound at a supply pressure of 0.15 MPaG and a rotation speed of 1700 rpm. Then, the first fluid and the second fluid were mixed in the thin film fluid.
- a silver fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged silver fine particle dispersion is centrifuged (18000 G for 20 minutes) to settle the silver fine particles, and after removing the supernatant liquid, washing with pure water is performed three times. Drying was performed at an atmospheric pressure of ° C. to prepare a dry powder of silver fine particles.
- Table 4 shows the average particle diameter of the silver fine particles obtained. (Shown as “particle diameter” in Table 4) and the coefficient of variation (CV) of the particle diameter.
- the temperature of the first fluid and the second fluid is adjusted to a temperature immediately before introducing each of the first fluid and the second fluid into the processing apparatus (more specifically, immediately before introducing between the processing surfaces 1 and 2). This is the temperature measured by heating and cooling.
- a TEM photograph of the silver fine particles obtained in the sample 11 is shown in FIG. 5, and a TEM photograph of the silver particles obtained in the sample 16 is shown in FIG. 8 shows changes in the particle diameter (average value) and coefficient of variation (C.V.) of the silver fine particles with respect to the ratio of water in the water-containing polyol used in the first fluid in Samples 8 to 16. Show.
- the first fluid of Sample 8 it takes 2 hours or more to dissolve 0.14 mol / LAgNO 3 in a polyol that does not contain water composed of ethylene glycol, and AgNO 3 exceeding 0.14 mol / L. could not be dissolved.
- AgNO 3 can be dissolved in the solvent in a short time, and the first fluid
- the ratio of water in the water-containing polyol contained in the fluid is increased, the concentration of AgNO 3 in the first fluid can be increased, and the amount of silver fine particles produced per unit time of the samples 11 to 16 is increased. Increased compared to Sample 8. From the above, it is possible to increase the amount of silver fine particles produced by including a water-containing polyol in the first fluid.
- a fluid containing a nickel compound and a fluid containing a reducing agent are disposed opposite to each other and are capable of approaching and separating.
- Mixing was performed in a thin film fluid formed between the processing surfaces 1 and 2 having at least one surface rotated with respect to the other, and nickel fine particles were produced as metal fine particles in the thin film fluid.
- a nickel fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged nickel fine particle dispersion is placed on a magnet, the nickel fine particles are allowed to settle, the supernatant liquid is removed, and then washing with pure water is performed three times. The resulting wet cake is subjected to atmospheric pressure at 25 ° C. To dry powder of nickel fine particles.
- the nickel fine particle powder after drying As a result of XRD measurement of the nickel fine particle powder after drying, it was found that it had a crystal structure consistent with FCC-type Ni, and further, there was no impurity from ICP measurement of a solution in which the powder was dissolved in nitric acid HNO 3 . It was found that nickel fine particles were produced. Further, the particle diameter of the nickel fine particles was confirmed by SEM observation, and the average value of the particle diameter and the coefficient of variation of the particle diameter were calculated. The crystallite diameter was calculated from X-ray diffraction (XRD) measurement. Tables 5 and 6 show the processing conditions (prescription and operating conditions) of the first fluid and the second fluid.
- Table 5 shows the amount of nickel fine particles produced per unit time (Ni production amount) and the ratio of water in the water-containing polyol used for the first fluid.
- Table 6 shows the average particle diameter of the nickel fine particles obtained. (Referred to as “particle diameter” in Table 6), coefficient of variation (CV) of particle diameter, and crystallite diameter.
- the temperatures of the first fluid and the second fluid are adjusted immediately before the first fluid and the second fluid are introduced into the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). (Heating / cooling) and measured temperature.
- NiSO 4 .6H 2 O is nickel sulfate hexahydrate
- DEG diethylene glycol
- PEG 600 is polyethylene glycol 600
- PW is pure water
- HMH is hydrazine monohydrate
- KOH water. Indicates potassium oxide.
- the water originally contained in the diethylene glycol used in this example was less than 0.5 wt%, the water originally contained is not considered.
- 9 shows changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 18 to 24. Show.
- the particle diameter of nickel fine particles, the coefficient of variation thereof, and the crystallite diameter can be controlled.
- the particle size and crystallite size of the nickel fine particles can be controlled to be increased by increasing the ratio of water in the water-containing polyol, and the nickel fine particles can be controlled by decreasing the ratio of water in the water-containing polyol. It was confirmed that the particle size and crystallite size can be controlled to be small. It was also confirmed that the coefficient of variation of the particle diameter of the nickel fine particles was less than 5% by controlling the ratio of water in the water-containing polyol to a range of 5 wt% to 60 wt%.
- the solvent of the first fluid of sample 17 is only a polyol, and the saturation solubility of the nickel compound (nickel sulfate hexahydrate) is low compared to the water-containing polyol which is the solvent of the first fluid of samples 18 to 24.
- the first fluid was prepared at room temperature (25 ° C.) and precipitates were generated immediately, nickel fine particles could not be produced using the first fluid of Sample 17. Therefore, it was determined that the first fluid of the sample 17 was inappropriate as a fluid used for producing nickel fine particles.
- concentration of the nickel sulfate hexahydrate in a 1st fluid can also be made high when the ratio of the water in the water-containing polyol contained in a 1st fluid is made high, the ratio of the water in a water-containing polyol is changed. By making it high, it became possible to increase the amount of nickel fine particles produced per unit time.
- the samples 25 to 31 each have a processing surface that can be approached and separated from each other and is arranged so that a fluid containing a nickel compound and a fluid containing a reducing agent are opposed to each other. Then, at least one was mixed in a thin film fluid formed between the processing surfaces 1 and 2 rotating with respect to the other to produce nickel fine particles as metal fine particles in the thin film fluid.
- a fluid containing a reducing agent is introduced between the processing surfaces 1 and 2 as a second fluid, The first fluid and the second fluid were mixed in the thin film fluid.
- a nickel fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged nickel fine particle dispersion is placed on a magnet, the nickel fine particles are allowed to settle, the supernatant liquid is removed, and then washing with pure water is performed three times. The resulting wet cake is subjected to atmospheric pressure at 25 ° C. To dry powder of nickel fine particles.
- the nickel fine particle powder had a crystal structure consistent with FCC type Ni, and further, there was no impurity from ICP measurement of a solution in which the powder was dissolved in nitric acid HNO 3 . It was found that nickel fine particles were produced. Further, the particle diameter of the nickel fine particles was confirmed by SEM observation, and the average value of the particle diameter and the coefficient of variation of the particle diameter were calculated. The crystallite diameter was calculated from X-ray diffraction (XRD) measurement. Tables 7 and 8 show the processing conditions (prescription and operating conditions) of the first fluid and the second fluid.
- Table 7 shows the amount of nickel fine particles produced per unit time (Ni production amount) and the ratio of water in the water-containing polyol used for the first fluid
- Table 8 shows the particle diameter of the obtained nickel fine particles.
- the average value (indicated as “particle diameter” in Table 8), the coefficient of variation (CV) of the particle diameter, and the crystallite diameter are shown.
- the temperatures of the first fluid and the second fluid are adjusted immediately before the first fluid and the second fluid are introduced into the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). (Heating / cooling) and measured temperature.
- NiSO 4 ⁇ 6H 2 O is nickel sulfate hexahydrate
- PG is propylene glycol
- PEG 600 is polyethylene glycol 600
- PW is pure water
- HMH is hydrazine monohydrate
- KOH Indicates potassium hydroxide.
- FIG. 10 shows changes in the particle diameter (particle diameter) and coefficient of variation (C.V.) of the nickel fine particles with respect to the ratio of water in the water-containing polyol used in the first fluid in samples 25 to 30. Show.
- the particle diameter of nickel fine particles, the coefficient of variation thereof, and the crystallite diameter can be controlled by controlling the ratio of water in the water-containing polyol contained in the first fluid.
- the particle diameter and crystallite diameter of the nickel fine particles can be increased by increasing the ratio of water in the water-containing polyol, and the nickel fine particles can be increased by decreasing the ratio of water in the water-containing polyol. It was confirmed that the particle size and crystallite size can be controlled to be small. It was also confirmed that the coefficient of variation of the particle diameter of the nickel fine particles was less than 5% by controlling the ratio of water in the water-containing polyol to a range of 5 wt% to 60%.
- concentration of the nickel sulfate hexahydrate in a 1st fluid can also be made high when the ratio of the water in the water-containing polyol contained in a 1st fluid is made high, the ratio of the water in a water-containing polyol is changed. By making it high, it became possible to increase the amount of nickel fine particles produced per unit time. Further, when the ratio of water in the water-containing polyol contained in the first fluid is increased, a reduction reaction can be performed under a condition in which the temperature of the first fluid is low, and as a result, the reaction temperature when depositing nickel fine particles is lowered. Therefore, it was confirmed that nickel fine particles can be produced at low cost and low energy as compared with the conventional manufacturing method.
- a fluid containing a nickel compound and a fluid containing a reducing agent are disposed so as to face each other and can be approached and separated. Then, at least one was mixed in a thin film fluid formed between the processing surfaces 1 and 2 rotating with respect to the other to produce nickel fine particles as metal fine particles in the thin film fluid.
- a nickel fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged nickel fine particle dispersion is placed on a magnet, the nickel fine particles are allowed to settle, the supernatant liquid is removed, and then washing with pure water is performed three times. The resulting wet cake is subjected to atmospheric pressure at 25 ° C. To dry powder of nickel fine particles.
- Table 10 shows the amount of nickel fine particles produced per unit time (Ni production amount) and the particle diameter of the obtained nickel fine particles.
- the average value (indicated as “particle diameter” in Table 10), the coefficient of variation (CV) of the particle diameter, the crystallite diameter, and the ratio of water in the water-containing polyol used for the second fluid are shown.
- the temperatures of the first fluid and the second fluid are adjusted immediately before the first fluid and the second fluid are introduced into the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). (Heating / cooling) and measured temperature.
- NiSO 4 ⁇ 6H 2 O is nickel sulfate hexahydrate
- EG is ethylene glycol
- PEG 600 polyethylene glycol 600
- PW is pure water
- HMH is hydrazine monohydrate
- KOH Indicates potassium hydroxide.
- FIG. 11 shows changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (CV) with respect to the ratio of water in the water-containing polyol used in the first fluid in Samples 32 to 36.
- the particle size, its coefficient of variation, and the crystallite size can be controlled by controlling the ratio of water in the water-containing polyol contained in the first fluid and the second fluid.
- the particle diameter and crystallite diameter of the nickel fine particles can be controlled to be small by reducing the ratio of water in the water, and from Examples 37, 38, 35, and 39, the water-containing polyol contained in the second fluid
- the ratio of water in the water-containing polyol contained in the first fluid By increasing the ratio of water, the particle diameter and crystallite diameter of the nickel fine particles can be controlled to be increased, and by reducing the ratio of water in the water-containing polyol, the particle diameter and crystallite diameter of the nickel fine particles are decreased. It was confirmed that control was possible. Further, from Examples 32 to 36, by controlling the ratio of water in the water-containing polyol contained in the first fluid to the range of 5 wt% to 60 wt%, the coefficient of variation of the particle diameter of the nickel fine particles is less than 5%.
- both the fluid containing at least one metal compound and the fluid containing at least one reducing agent contain a water-containing polyol, and the ratio of water in the water-containing polyol contained in either one of the two is controlled. By doing so, it was confirmed that the particle diameter of nickel fine particles and the coefficient of variation thereof could be controlled.
- a fluid containing a nickel compound and a fluid containing a reducing agent are disposed so as to face each other and can be approached and separated. Then, at least one was mixed in a thin film fluid formed between the processing surfaces 1 and 2 rotating with respect to the other to produce nickel fine particles as metal fine particles in the thin film fluid.
- a nickel fine particle dispersion was discharged from between the processing surfaces 1 and 2. The discharged nickel fine particle dispersion is placed on a magnet, the nickel fine particles are allowed to settle, the supernatant liquid is removed, and then washing with pure water is performed three times. The resulting wet cake is subjected to atmospheric pressure at 25 ° C. To dry powder of nickel fine particles.
- Table 11 shows the ratio of water in the water-containing polyol used for the first fluid, the average value of the particle diameters of nickel fine particles obtained in Table 12 (indicated as “particle diameter” in Table 12), and the particle diameter.
- the coefficient of variation (CV), crystallite diameter, and the amount of nickel fine particles produced per unit time (Ni production amount) are shown.
- the temperatures of the first fluid and the second fluid are adjusted immediately before the first fluid and the second fluid are introduced into the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). (Heating / cooling) and measured temperature.
- Ni (NO 3 ) 2 ⁇ 6H 2 O is nickel nitrate hexahydrate
- EG is ethylene glycol
- BYK-154 is Disper Big BYK-154 (dispersant manufactured by Big Chemie)
- PW represents pure water
- HMH represents hydrazine monohydrate
- KOH represents potassium hydroxide.
- the water originally contained in the ethylene glycol used in this example was less than 1.0 wt%, the water originally contained is not considered. 13 shows changes in the particle diameter (average value) of nickel fine particles and the coefficient of variation (C.V.) of the particle diameter with respect to the ratio of water in the water-containing polyol used for the first fluid in Samples 40 to 45. .
- the particle size of nickel fine particles, its coefficient of variation, and the crystallite size can be controlled by controlling the ratio of water in the water-containing polyol contained in the first fluid.
- the particle size and crystallite size of the nickel fine particles can be controlled to be increased by increasing the ratio of water in the water-containing polyol, and the nickel fine particles can be controlled by decreasing the ratio of water in the water-containing polyol. It was confirmed that the particle size and crystallite size can be controlled to be small. It was also confirmed that the coefficient of variation of the particle diameter of the nickel fine particles was less than 5% by controlling the ratio of water in the water-containing polyol to a range of 5 wt% to 60%.
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Abstract
Description
また、特許文献5には、炭素数4以下の1価のアルコールとポリオールとの混合溶媒と、水との混合液を用いる方法が提案されているが、混合溶媒と水との混合比率を制御することにより、析出する金属粉末の粒径を制御することは記載されているが、析出する金属粉末の粒径の変動係数を5%未満に制御する旨の記載はない。
また、本発明は、上記水含有ポリオールに含まれる水の比率を5wt%~60wt%の範囲に制御することによって、上記変動係数を5%未満に制御するものとして実施することができる。
また、本発明は、上記少なくとも1種類の金属及び/又は金属化合物を含む流体と、上記少なくとも1種類の還元剤を含む流体との、何れか一方の被処理流動体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないものとして実施することができ、上記少なくとも1種類の金属及び/又は金属化合物を含む流体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないものとして実施することができる。
また、本発明は、上記少なくとも1種類の金属及び/又は金属化合物を含む流体と、上記少なくとも1種類の還元剤を含む流体との、双方の被処理流動体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないものとして実施することができる。
また、本発明は、上記少なくとも1種類の金属化合物がニッケル化合物であり、上記少なくとも1種類の還元剤がニッケルを析出させるための還元剤であり、上記析出させるニッケル微粒子の粒子径の平均値が350nm以下であるものとして実施することができる。
本発明における金属は、特に限定されない。化学周期表上における全ての金属である。一例として、Ti、Fe、W、Pt、Au、Cu、Ag、Pd、Ni、Mn、Co、Ru、V、Zn、Zr、Sn、In、Te、Ta、Bi、Sbなどの金属元素が挙げられる。それらの金属について、単体元素の金属であっても、複数元素を含む合金や金属元素に非金属元素を含む物質であっても良い。当然、卑金属と貴金属の合金としても実施できる。
本発明における金属化合物としては、特に限定されない。一例としては、金属の塩、酸化物、水酸化物、水酸化酸化物、窒化物、炭化物、錯体、有機塩、有機錯体、有機化合物またはそれらの水和物、有機溶媒和物などが挙げられる。金属の塩としては特に限定されないが、金属の硝酸塩や亜硝酸塩、硫酸塩や亜硫酸塩、蟻酸塩や酢酸塩、リン酸塩や亜リン酸塩、次亜リン酸塩や塩化物、オキシ塩やアセチルアセトナート塩またはそれらの水和物、有機溶媒和物などが挙げられる。これらの金属化合物は、それぞれ単独で用いても良く、複数の混合物として用いても良い。
本発明に用いる還元剤としては、金属及び/または金属化合物、好ましくは金属イオンを還元することができる物質であり、特に限定されないが、ヒドラジンまたはヒドラジン一水和物、ホルムアルデヒドスルホキシル酸ナトリウム、水素化ホウ素金属塩、水素化アルミニウム金属塩、水素化トリエチルホウ素金属塩、グルコース、クエン酸、アスコルビン酸、タンニン酸、ジメチルホルムアミド、テトラブチルアンモニウムボロヒドリド、次亜リン酸ナトリウム(NaH2PO2)、金属の化合物またはそれらのイオン、好ましくは遷移金属の化合物またはそれらのイオン(鉄、チタンなど)などが挙げられる。上記の還元剤は、それぞれ単独で用いても良く、複数の混合物として用いても良い。
また、本発明においては、少なくとも1種類の還元剤を含む流体を用いるものであり、少なくとも1種類の上記の還元剤を、溶媒と混合し、溶解または分子分散して用いることが好ましい。
そして、少なくとも1種類の金属及び/又は金属化合物を含む流体と、少なくとも1種類の還元剤を含む流体との、少なくとも何れか一方の流体は、後述する水含有ポリオールを含み、かつ、メタノールやエタノールなどの1価のアルコールを含まないものであり、少なくとも1種類の金属及び/又は金属化合物を含む流体に用いられる溶媒と、少なくとも1種類の還元剤を含む流体に用いられる溶媒との、少なくとも何れか一方の溶媒に、当該水含有ポリオールを用いることが好ましい。
本発明に用いる水含有ポリオールは、水とポリオールとを混合させたものである。水としては特に限定されないが、イオン交換水やRO水、純水や超純水などが挙げられる。また、ポリオールは、2価以上のアルコールであり、エチレングリコールやプロピレングリコール、トリメチレングリコールやテトラエチレングリコール、またはジエチレングリコールやグリセリン、ポリエチレングリコールやポリプロピレングリコールなどが挙げられる。
粒子径の変動係数とは、得られる金属微粒子の均一さの度合いを表す指標となるものであり、金属微粒子の粒子径分布における平均粒子径と標準偏差とから、変動係数(C.V.)(%)=標準偏差÷平均粒子径×100の式にて求められる。この変動係数の値が小さいほど得られる金属微粒子の粒子径の分布は狭く、金属微粒子としての均一性が高い。また、この変動係数の値が大きいほど金属微粒子としての均一性が低いため、例えば工業的に用いるには、必要なサイズの粒子径の金属微粒子以外を分級作業で取り除く必要があるなどの問題が発生する場合がある。
ポリオール還元法での還元力は、一般的に、還元する際の温度や、金属塩の種類、ポリオールの種類などに依存する。本発明においては、還元温度や金属塩の種類、ポリオールの種類による還元力の制御とともに、水含有ポリオールに含まれる水の比率を制御することによって、作製する金属微粒子の粒子径及びその変動係数を制御することができると、本願出願人は考える。ここで、ポリオール還元法とは、ポリオールによる金属イオンの還元のほかポリオールと別途の還元剤とを併用する金属イオンの還元をも含めたものを言う。
本発明においては、得られる金属微粒子の粒子径の制御は、水含有ポリオール中の水の比率を高くすることで粒子径が大きくなるよう制御し、水含有ポリオール中の水の比率を低くすることで粒子径が小さくなるよう制御することが好ましい。また、本発明においては、得られる金属微粒子の粒子径の変動係数の制御は、水含有ポリオール中の水の比率を5wt%~60wt%の範囲に制御することで粒子径の変動係数を5%未満に制御することが好ましい。
そして、少なくとも1種類の金属及び/又は金属化合物を水含有ポリオールに溶解して、少なくとも1種類の金属及び/または金属化合物を含む流体とすることが好ましい。一般的に、ポリオールのみを溶媒として用いた場合、水のみを溶媒として用いた場合と比べ、金属及び/または金属化合物の溶解度が低い。水含有ポリオールを溶媒に用いることよって、ポリオールのみを溶媒として用いた場合と比べて、少なくとも1種類の金属及び/または金属化合物を含む流体中の金属及び/または金属化合物の濃度を高くすることができ、特に、後述する流体処理装置のような連続生産可能な装置を用いた場合には、その生産量並びに生産効率を飛躍的に向上させることが可能である。
本発明においては、水含有ポリオール中の水の比率を、5wt%~60wt%の範囲に制御することが好ましく、10wt%~55wt%の範囲に制御することがより好ましい。得られる金属微粒子の粒子径の変動係数を5%未満に制御することが可能である。水含有ポリオール中の水の比率が5wt%~60wt%の範囲を超えると、得られる金属微粒子の粒子径の変動係数が5%以上となる。要因としては、水含有ポリオール中の水とポリオールとの混合比率とポリオールの還元能とが、金属微粒子の粒子径の変動係数に影響しているためと、本願出願人は考える。
また、水を混合することによってポリオールの引火性液体としての危険性を低減できる利点があり、水含有ポリオール中の水の比率が40wt%を超える場合には、危険物の適用の対象外とできる利点がある。
本発明に用いる水含有ポリオール以外の溶媒は、特に限定されず、種々の溶媒を用いることができる。水含有ポリオール以外の溶媒としては、特に限定されないが、上述した水含有ポリオールに用いられる水やポリオール、メタノールやエタノールのようなアルコール系有機溶媒、アセトンやメチルエチルケトンのようなケトン系有機溶媒、酢酸エチルや酢酸ブチルのようなエステル系有機溶媒、ジメチルエーテルやジブチルエーテルなどのエーテル系有機溶媒、ベンゼンやトルエン、キシレンなどの芳香族系有機溶媒、ヘキサンや、ペンタンなどの脂肪族炭化水素系有機溶媒などが挙げられる。また、水含有ポリオール以外の溶媒として、後述する酸性物質を用いてもよい。上記の溶媒はそれぞれ単独で使用しても良く、複数を混合して使用しても良い。
また、本発明においては、水含有ポリオールに、水とポリオール以外の溶媒を、本発明に影響しない程度に用いてもよく、また、用いなくてもよい。水とポリオール以外の溶媒としては、アセトンやメチルエチルケトンのようなケトン系有機溶媒、酢酸エチルや酢酸ブチルのようなエステル系有機溶媒、ジメチルエーテルやジブチルエーテルなどのエーテル系有機溶媒、ベンゼンやトルエン、キシレンなどの芳香族系有機溶媒、ヘキサンや、ペンタンなどの脂肪族炭化水素系有機溶媒などが挙げられる。上記の溶媒はそれぞれ単独で使用しても良く、複数を混合して使用しても良い。
また、上記のアルコール系有機溶媒やポリオールを溶媒として用いた場合には、溶媒そのものが還元剤としても働く利点がある。
しかしながら、本発明の制御を簡易に実行する上で、被処理流動体に1価のアルコールを含まない方が有利である。
本発明においては、少なくとも1種類の金属及び/または金属化合物を含む流体と、少なくとも1種類の還元剤を含む流体とを、接近・離反可能に互いに対向して配設され、少なくとも一方が他方に対して回転する処理用面の間にできる、薄膜流体中で混合する方法を用いて行うことが好ましく、例えば、特許文献6に示される装置と同様の原理の装置を用いて混合する事によって金属微粒子を析出させることが好ましい。
この鏡面研磨の面粗度は、特に限定されないが、好ましくはRa0.01~1.0μm、より好ましくはRa0.03~0.3μmとする。
このように、3次元的に変位可能に保持するフローティング機構によって、第2処理用部20を保持することが望ましい。
P=P1×(K-k)+Ps
なお、図示は省略するが、近接用調整面24を離反用調整面23よりも広い面積を持ったものとして実施することも可能である。
レイノルズ数Re=慣性力/粘性力=ρVL/μ=VL/ν
ここで、ν=μ/ρは動粘度、Vは代表速度、Lは代表長さ、ρは密度、μは粘度を示す。
そして、流体の流れは、臨界レイノルズ数を境界とし、臨界レイノルズ数以下では層流、臨界レイノルズ数以上では乱流となる。
上記流体処理装置の両処理用面1,2間は微小間隔に調整されるため、両処理用面1,2間に保有される流体の量は極めて少ない。そのため、代表長さLが非常に小さくなり、両処理用面1,2間を通過する薄膜流体の遠心力は小さく、薄膜流体中は粘性力の影響が大きくなる。従って、上記のレイノルズ数は小さくなり、薄膜流体は層流となる。
遠心力は、回転運動における慣性力の一種であり、中心から外側に向かう力である。遠心力は、以下の式で表される。
遠心力F=ma=mv2/R
ここで、aは加速度、mは質量、vは速度、Rは半径を示す。
上述の通り、両処理用面1,2間に保有される流体の量は少ないため、流体の質量に対する速度の割合が非常に大きくなり、その質量は無視できるようになる。従って、両処理用面1,2間にできる薄膜流体中においては重力の影響を無視できる。そのため、本来微粒子として析出させることが難しい比重差のある2種以上の金属元素を含む合金や複合金属化合物などの微粒子においても、両処理用面1,2間にできる薄膜流体中で析出させることができる。
この凹部13の先端と第1処理用面1の外周面との間には、凹部13のない平坦面16が設けられている。
円環形状の開口部d20を処理用面2の中央の開口を取り巻く同心円状に設けた場合、処理用面1,2間に導入する第2流体を同一条件で導入することができるため、より均一な拡散・反応・析出等の流体処理を行うことができる。微粒子を量産する場合には、開口部を円環形状とすることが好ましい。
さらに、第1、第2流体等の被処理流動体の温度を制御したり、第1流体と第2流体等との温度差(即ち、供給する各被処理流動体の温度差)を制御することもできる。供給する各被処理流動体の温度や温度差を制御するために、各被処理流動体の温度(処理装置、より詳しくは、処理用面1,2間に導入される直前の温度)を測定し、処理用面1,2間に導入される各被処理流動体の加熱又は冷却を行う機構を付加して実施することも可能である。
本発明において、少なくとも1種類の金属及び/または金属化合物を含む流体や少なくとも1種類の還元剤を含む流体のpHは、特に限定されない。用いる金属及び/または金属化合物や還元剤の種類や濃度、目的や対象となる金属種などによって、適宜変更する事が可能である。
また、本発明においては、目的や必要に応じて各種分散剤や界面活性剤を用いる事ができる。特に限定されないが、界面活性剤及び分散剤としては一般的に用いられる様々な市販品や、製品または新規に合成したものなどを使用できる。特に限定されないが、陰イオン性界面活性剤、陽イオン性界面活性剤、非イオン性界面活性剤や、各種ポリマーなどの分散剤などを挙げることができる。これらは単独で使用してもよく、2種以上を併用してもよい。また、ポリエチレングリコールやポリプロピレングリコールなどをポリオールとして用いた場合には、ポリオールが分散剤としても作用する。
本発明において、少なくとも1種類の金属及び/または金属化合物を含む流体と少なくとも1種類の還元剤を含む流体とを混合する際の温度は、特に限定されない。用いる金属及び/又は金属化合物の種類や還元剤の種類、対象とする金属種やそれぞれの流体のpHなどによって適切な温度で実施することが可能である。
また、本発明における金属微粒子は、酸化物や水酸化物、酸化水酸化物などを一部含んでも実施できる。
走査型電子顕微鏡(SEM)観察には、電界放射型走査電子顕微鏡(FE-SEM):日本電子製のJSM-7500Fを使用し、得られた金属微粒子粉体を観察した。観察条件としては、加速電圧を15kV、観察倍率を5千倍以上とし、粒子径については、SEM観察にて確認された金属微粒子の一次粒子径を粒子径とし、100個の一次粒子径の平均値を粒子径の平均値として採用した。また、変動係数(C.V.)を、C.V.=標準偏差÷粒子径の平均値×100(%)にて算出した。
(X線回折測定)
X線回折(XRD)測定には、粉末X線回折測定装置 X‘Pert PRO MPD(XRD スペクトリス PANalytical事業部製)を使用した。測定条件は,Cu対陰極,管電圧45kV,管電流40mA,0.016step/10sec、測定範囲は10~100[°2Theta](Cu)である。得られたニッケル微粒子の乾燥粉体の結晶子径をXRD測定結果より算出した。シリコン多結晶盤は、47.3℃に確認されるピークを使用し、得られたニッケル回折パターンの44.5°付近のピークにScherrer式 D=K・λ/(β・cosθ)を当てはめた。
ここで、KはScherrer定数であり、K=0.9とする。λは使用したX線管球の波長、βは半値幅、θは回折角を用いて算出した。
透過電子顕微鏡(TEM)観察には、透過型電子顕微鏡、JEM-2100(JEOL製)を用い、得られた金属微粒子粉体を観察した。観察条件としては、加速電圧を200kV、観察倍率を3万倍以上とし、粒子径については、TEM観察にて確認された金属微粒子の一次粒子径を粒子径とし、100個の一次粒子径の平均値を粒子径の平均値として採用した。また、変動係数(C.V.)を、C.V.=標準偏差÷粒子径の平均値×100(%)にて算出した。
表1及び表2に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表1に第1流体に用いた水含有ポリオール中の水の比率を、表2に得られたニッケル微粒子の粒子径の平均値(表2には「粒子径と表記」)と粒子径の変動係数(C.V.)、結晶子径を示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)に温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、NiSO4・6H2Oは硫酸ニッケル六水和物、EGはエチレングリコール、PEG600はポリエチレングリコール600、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたエチレングリコールに元々含まれる水は1.0wt%未満であったため、元々含まれる水については、考慮しない。また、試料4において得られたニッケル微粒子のSEM写真を図4に示す。また、図7に試料1~7にて第1流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(平均値)及び粒子径の変動係数(C.V.)の変化を示す。
また、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体の温度が低い条件で還元反応が可能となり、結果として、ニッケル微粒子を析出させる際の反応温度を低くすることができるため、従来の製造方法と比べて、低コスト、低エネルギーでニッケル微粒子を作製できることを確認した。
一方、溶媒として水を含有しないポリオールを用いた試料1の第1流体は、第1流体を室温(25℃)で調製してから30分間経過後に析出物が生じ、その後、試料1の第1流体を加熱してもその析出物は溶解しなかった。よって、試料1の第1流体は、ニッケル微粒子作製に用いる流体としては不適切であると判断した。
表3、表4に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表3に単位時間当たりの銀微粒子の生成量(Ag生成量)と第1流体に用いた水含有ポリオール中の水の比率を、表4に得られた銀微粒子の粒子径の平均値(表4では「粒子径」と表記)と粒子径の変動係数(C.V.)を示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)に温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、AgNO3は硝酸銀、EGはエチレングリコール、PVP(K=30)はポリビニルピロリドン(K=30)、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたエチレングリコールに元々含まれる水は1.0wt%未満であったため、元々含まれる水については、考慮しない。また、試料11において得られた銀微粒子のTEM写真を図5に、試料16において得られた銀粒子のTEM写真を図6に示す。また、図8に試料8~16にて第1流体に用いた水含有ポリオール中の水の比率に対する銀微粒子の粒子径(平均値)及び粒子径の変動係数(C.V.)の変化を示す。
試料8,13、14、15、16においては、銀微粒子分散液を処理用面1,2間より吐出させた後、10分程度で明らかに銀微粒子分散液中の銀微粒子が凝集する様子が確認され、図6に示すように、見かけ上、凝集・融着した銀粒子が確認された。一方、試料9~12においては、吐出後10分程度で銀微粒子分散液中の銀微粒子が凝集する様子は確認できなかった。よって、水含有ポリオール中の水の比率が5wt%~60wt%の範囲でエチレングリコールと純水とを混合した水含有ポリオールを用いることで、分離の良い銀微粒子を効率よく作製することが可能であることがわかった。
また、試料8の第1流体において、エチレングリコールよりなる水を含まないポリオールへの0.14mol/LAgNO3の溶解には、2時間以上の時間を要し、0.14mol/Lを超えるAgNO3を溶解することはできなかった。しかしながら、試料9~16のように、第1流体の溶媒としてエチレングリコールと純水とを混合させた水含有ポリオールを用いることによって、AgNO3の溶媒への溶解が短時間で行えるとともに、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体中のAgNO3の濃度を高くすることが可能となり、試料11~16の単位時間当たりに作製される銀微粒子の生成量は、試料8と比べて多くなった。以上のことから、第1流体に水含有ポリオールを含むことによって、銀微粒子の生成量を増大させることが可能となった。
表5及び表6に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表5に単位時間当たりのニッケル微粒子の生成量(Ni生成量)と第1流体に用いた水含有ポリオール中の水の比率を、表6に得られたニッケル微粒子の粒子径の平均値(表6では「粒子径」と表記)と粒子径の変動係数(C.V.)、結晶子径を示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)にて温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、NiSO4・6H2Oは硫酸ニッケル六水和物、DEGはジエチレングリコール、PEG600はポリエチレングリコール600、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたジエチレングリコールに元々含まれる水は0.5wt%未満であったため、元々含まれる水については、考慮しない。また、図9に試料18~24にて第1流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(平均値)及び粒子径の変動係数(C.V.)の変化を示す。
試料17の第1流体の溶媒はポリオールのみであり、試料18~24の第1流体の溶媒である水含有ポリオールに比べて、ニッケル化合物(硫酸ニッケル六水和物)の飽和溶解度が低いだけでなく、第1流体を室温(25℃)で調製して直ぐに析出物が生じたため、試料17の第1流体を用いてニッケル微粒子を作製することができなかった。よって、試料17の第1流体は、ニッケル微粒子作製に用いる流体としては不適切であると判断した。
また、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体中の硫酸ニッケル六水和物の濃度も高くすることができるため、水含有ポリオール中の水の比率を高くすることによって、単位時間当たりに作製されるニッケル微粒子の生成量を増大させることが可能となった。
試料18~24においては、第1流体の温度、第2流体の温度ともに同じ温度で実施したが、第1流体に含まれる水含有ポリオール中の水の比率を制御することによって、ニッケル微粒子の粒子径及びその変動係数を制御できることや、水含有ポリオール中の水の比率を5wt%~60wt%の範囲に制御することによって、ニッケル微粒子の粒子径の変動係数が5%未満となることを確認した。
表7及び表8に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表7には単位時間当たりのニッケル微粒子の生成量(Ni生成量)と第1流体に用いた水含有ポリオール中の水の比率を、表8には得られたニッケル微粒子の粒子径の平均値(表8では「粒子径」と表記)と粒子径の変動係数(C.V.)、結晶子径を示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)にて温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、NiSO4・6H2Oは硫酸ニッケル六水和物、PGはプロピレングリコール、PEG600はポリエチレングリコール600、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたプロピレングリコールに元々含まれる水は1.0wt%未満であったため、元々含まれる水については、考慮しない。また、図10に試料25~30にて第1流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(粒子径)及び粒子径の変動係数(C.V.)の変化を示す。
また、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体中の硫酸ニッケル六水和物の濃度も高くすることができるため、水含有ポリオール中の水の比率を高くすることによって、単位時間当たりに作製されるニッケル微粒子の生成量を増大させることが可能となった。また、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体の温度が低い条件で還元反応が可能となり、結果として、ニッケル微粒子を析出させる際の反応温度を低くすることができるため、従来の製造方法と比べて、低コスト、低エネルギーでニッケル微粒子を作製することができることを確認した。
一方、試料25においては、第1流体調整後に析出物を生じなかったが、第1流体の調製に5時間を要した。また、溶解時間に9時間以上の長時間を要すれば、プロピレングリコールに硫酸ニッケル六水和物が20wt%程度溶解することについても確認したが、現実的でないと判断した。また試料31においては、プロピレングリコールを全く用いずに、ニッケル微粒子の作製を試みたが、還元が十分に行われず、ニッケル微粒子の作製が不可能であった。
表9及び表10に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表9には第1流体に用いた水含有ポリオール中の水の比率、表10には、単位時間当たりのニッケル微粒子の生成量(Ni生成量)と、得られたニッケル微粒子の粒子径の平均値(表10では「粒子径」と表記)と粒子径の変動係数(C.V.)、結晶子径、第2流体に用いた水含有ポリオール中の水の比率を示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)にて温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、NiSO4・6H2Oは硫酸ニッケル6水和物、EGはエチレングリコール、PEG600はポリエチレングリコール600、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたエチレングリコールに元々含まれる水は1.0wt%未満であったため、元々含まれる水については、考慮しない。また、図11に試料32~36にて第1流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(平均値)及びその変動係数(C.V.)の変化を、図12に試料37、38、35、39にて第2流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(平均値)及び粒子径の変動係数(C.V.)の変化を示す。
また、試料32~36においては、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体の温度が低い条件で還元反応が可能となり、結果として、ニッケル微粒子を析出させる際の反応温度を低くすることができるため、従来の製造方法と比べて、低コスト、低エネルギーでニッケル微粒子を作製できることを確認した。
さらに、少なくとも1種類の金属化合物を含む流体と少なくとも1種類の還元剤を含む流体の双方に水含有ポリオールを含み、双方のうちの何れか一方に含まれる水含有ポリオール中の水の比率を制御することによって、ニッケル微粒子の粒子径及びその変動係数を制御できることを確認した。
表11及び表12に、第1流体と第2流体の処理条件(処方及び運転条件)を示す。また、表11には第1流体に用いた水含有ポリオール中の水の比率を、表12に得られたニッケル微粒子の粒子径の平均値(表12では「粒子径」と表記)と粒子径の変動係数(C.V.)、結晶子径、単位時間当たりのニッケル微粒子の生成量(Ni生成量)とを示す。また、第1流体及び第2流体の温度は、第1流体と第2流体のそれぞれを処理装置に導入する直前(より詳しくは、処理用面1,2間に導入する直前)にて温調(加熱・冷却)して、測定した温度である。
ここで、表中における略記号は、Ni(NO3)2・6H2Oは硝酸ニッケル6水和物、EGはエチレングリコール、BYK-154はディスパービッグBYK-154(ビックケミー社製分散剤)、PWは純水、HMHはヒドラジン一水和物、KOHは水酸化カリウムを示す。また、本実施例に用いたエチレングリコールに元々含まれる水は1.0wt%未満であったため、元々含まれる水については、考慮しない。また、図13に試料40~45において第1流体に用いた水含有ポリオール中の水の比率に対するニッケル微粒子の粒子径(平均値)と粒子径の変動係数(C.V.)の変化を示す。
また、第1流体に含まれる水含有ポリオール中の水の比率を高くすると、第1流体の温度が低い条件で還元反応が可能となり、結果として、ニッケル微粒子を析出させる際の反応温度を低くすることができるため、従来の製造方法と比べて、低コスト、低エネルギーでニッケル微粒子を作製できることを確認した。
2 第2処理用面
10 第1処理用部
11 第1ホルダ
20 第2処理用部
21 第2ホルダ
d1 第1導入部
d2 第2導入部
d20 開口部
Claims (9)
- 少なくとも2種類の被処理流動体を用いるものであり、
そのうちで少なくとも1種類の被処理流動体は、少なくとも1種類の金属及び/又は金属化合物を含む流体であり、
上記以外の被処理流動体で少なくとも1種類の被処理流動体は、少なくとも1種類の還元剤を含む流体であり、
上記の被処理流動体を、対向して配設された、接近・離反可能な、少なくとも一方が他方に対して相対的に回転する少なくとも2つの処理用面間にできる薄膜流体中で混合し、金属微粒子を析出させるものであり、
上記少なくとも1種類の金属及び/又は金属化合物を含む流体と、上記少なくとも1種類の還元剤を含む流体との、少なくとも何れか一方の被処理流動体は、水とポリオールとを混合させた水含有ポリオールを含み、かつ、1価のアルコールを含まないものであり、
上記水含有ポリオールに含まれる水の比率を制御することによって、析出させる金属微粒子の粒子径及びその変動係数を制御することを特徴とする、金属微粒子の製造方法。 - 上記水含有ポリオールに含まれる水の比率を5wt%~60wt%の範囲に制御することによって、上記変動係数を5%未満に制御することを特徴とする、請求項1に記載の金属微粒子の製造方法。
- 上記ポリオールが、エチレングリコール、プロピレングリコール、トリメチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ジエチレングリコール、グリセリン、ポリプロピレングリコールから選ばれる少なくとも何れか1種であることを特徴とする、請求項1または2に記載の金属微粒子の製造方法。
- 上記少なくとも1種類の金属及び/又は金属化合物を含む流体と、上記少なくとも1種類の還元剤を含む流体との、何れか一方の被処理流動体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないことを特徴とする、請求項1~3の何れかに記載の金属微粒子の製造方法。
- 上記少なくとも1種類の金属及び/又は金属化合物を含む流体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないことを特徴とする、請求項4に記載の金属微粒子の製造方法。
- 上記少なくとも1種類の金属及び/又は金属化合物を含む流体と、上記少なくとも1種類の還元剤を含む流体との、双方の被処理流動体は、上記水含有ポリオールを含み、かつ、1価のアルコールを含まないことを特徴とする、請求項1~3の何れかに記載の金属微粒子の製造方法。
- 上記少なくとも1種類の金属及び/又は金属化合物を含む流体と上記少なくとも1種類の還元剤を含む流体とのうちの何れか一方の被処理流動体が、上記薄膜流体を形成しながら上記両処理用面間を通過し、
上記何れか一方の被処理流動体が流される流路とは独立した別途の導入路を備えており、
上記少なくとも2つの処理用面の少なくとも何れか一方に上記別途の導入路に通じる開口部を少なくとも一つ備え、
上記少なくとも1種類の金属及び/又は金属化合物を含む流体と上記少なくとも1種類の還元剤を含む流体とのうちの何れか他方の被処理流動体を、上記開口部から上記少なくとも2つの処理用面の間に導入して、上記少なくとも1種類の金属及び/又は金属化合物を含む流体と上記少なくとも1種類の還元剤を含む流体とを、上記薄膜流体中で混合することを特徴とする、請求項1~6の何れかに記載の金属微粒子の製造方法。 - 上記金属及び/又は金属化合物は、ニッケル、銀、ニッケル化合物、銀化合物から選ばれる少なくとも何れか1種であり、
上記還元剤は、ニッケル、銀から選ばれる少なくとも何れか1種を析出させるための還元剤であることを特徴とする、請求項1~7の何れかに記載の金属微粒子の製造方法。 - 上記少なくとも1種類の金属化合物がニッケル化合物であり、上記少なくとも1種類の還元剤がニッケルを析出させるための還元剤であり、上記析出させるニッケル微粒子の粒子径の平均値が350nm以下であることを特徴とする、請求項1~8の何れかに記載の金属微粒子の製造方法。
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US20160256930A1 (en) * | 2015-03-02 | 2016-09-08 | Polyvalor, Société En Commandite | Alloy nanoparticles, process for their preparation and use thereof |
JP2020041197A (ja) * | 2018-09-12 | 2020-03-19 | 住友金属鉱山株式会社 | ニッケル粉末およびニッケル粉末の製造方法 |
JPWO2021220552A1 (ja) * | 2020-04-28 | 2021-11-04 |
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WO2014041706A1 (ja) * | 2012-09-12 | 2014-03-20 | エム・テクニック株式会社 | ニッケル微粒子の製造方法 |
CA2996403A1 (en) | 2015-10-05 | 2017-04-13 | M. Technique Co., Ltd. | Metal oxide particles and method of producing the same |
CN114621681B (zh) * | 2016-06-02 | 2023-07-18 | M技术株式会社 | 透明材料用紫外线和/或近红外线遮断剂组合物 |
JP2022134575A (ja) * | 2021-03-03 | 2022-09-15 | 戸田工業株式会社 | 軟磁性金属粉末 |
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Cited By (6)
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US20160256930A1 (en) * | 2015-03-02 | 2016-09-08 | Polyvalor, Société En Commandite | Alloy nanoparticles, process for their preparation and use thereof |
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JP2020041197A (ja) * | 2018-09-12 | 2020-03-19 | 住友金属鉱山株式会社 | ニッケル粉末およびニッケル粉末の製造方法 |
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KR101988239B1 (ko) | 2019-06-12 |
KR20150054984A (ko) | 2015-05-20 |
US20150246395A1 (en) | 2015-09-03 |
US9821375B2 (en) | 2017-11-21 |
EP2896474B1 (en) | 2019-01-16 |
JP2014074222A (ja) | 2014-04-24 |
JP5831821B2 (ja) | 2015-12-09 |
EP2896474A1 (en) | 2015-07-22 |
CN104640653A (zh) | 2015-05-20 |
EP2896474A4 (en) | 2016-04-06 |
CN104640653B (zh) | 2016-06-15 |
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