CN101830497B - Supergravity hydrothermal preparation method of spherical inorganic powder grains - Google Patents
Supergravity hydrothermal preparation method of spherical inorganic powder grains Download PDFInfo
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Abstract
The invention relates to a supergravity hydrothermal preparation method of spherical inorganic powder grains, which comprises the following steps: preparing a metal salt solution at a concentration of 0.001 to 2mol/L; adding a S<2-> chemical reagent into the obtained solution, and adjusting the pH value of the solution to dissolve the S<2-> chemical reagent, wherein the molar ratio of the metal salt ions to the sulfur ions is 1:1 to 1:5; adding an organic solvent or aqueous high polymer compound into the obtained solution, wherein the volume ratio of the organic solvent or aqueous high polymer compound to the metal salt solution is 1:1 to 1:50; pouring the mixed solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, fixing the high-pressure reaction kettle on a fixed bracket in a hearth, and performing a hydrothermal reaction in the presence of supergravity at 50 to 250 DEG C for 0.1 to 5 hours under the action of a relative centrifugal force of 100 to 10,000 grams; and filtering the reaction product, washing the reaction product, and drying the reaction product under vacuum to obtain the needed product. The spherical inorganic powder grains prepared by the invention have the characteristics of high roundness, monodispersion and narrow distribution. The inorganic powder prepared by the method of the invention comprises ZnS, CdS, CuS, PbS, and the like. The inorganic powder grains can be used for manufacturing photonic crystals, rare earth luminescent materials, phononic crystals, solar materials, left-handed materials and the like.
Description
Technical field
The present invention relates to a kind of supergravity hydrothermal preparation method of inorganic spherical powder particle.
Background technology
In recent years; (like quantum effect and special light, electrical property etc.) obtain increasing application in high-tech sector because the many characteristics of himself to have nanometer or the sub-micron ball of monodispersity; Can be used for making the storage of microreactor and discharge device like it; The loading slowly-releasing instrument of medicine, dyestuff and makeup, the protector of bioactive macromolecule, catalyzer, the separation of refuse and the filling of material etc.In addition, the monodispersity bead that three-dimensional order is arranged also shows performances such as special light, sound, can be used for making photon, phonon crystal material etc.
[1-2]The research of at present relevant spheroidal particle mainly concentrates on nanometer or the submicron hollow ball, and the method for employing mainly contains jet nozzle reactors method, emulsion/phase detachment technique, emulsion interfacial polymerization, self-assembly process, aerosol cracking process and template etc.
[3-5]And the research of relevant high circularity, dispersed nano or submicron solid sphere report seldom.Because crystal grain difference of the speed of growth on all directions in process of growth is difficult to make spheroidal particle, particularly submicron solid sphere particle in the aqueous solution.
Hypergravity is the big many power of a kind of force of gravity that when axle is made centrifugal motion, is produced by object; When promptly a material that pivots rotates with certain speed; After rotating speed reaches certain value; The cf-that material receives will be more much bigger than its gravity, and the much bigger power of this force of gravity is exactly hypergravity.Long ago, people utilize the hypergravity of centrifugal generation to carry out scientific research with regard to beginning, and have developed equipment such as whizzer, sol evenning machine.Along with the researchdevelopment of nanometer material science, the application of centrifugation technique in material prepn research obtained paying attention to gradually in recent years.Wang Qudong etc.
[6]Adopt the growth morphology of primary crystal Si in the centrifugal liquid method research hypereutectic Al-Si alloy that inclines, found primary crystal Si presence bit faulting of slab ends rank growth mechanism, and successfully explained the branch of primary crystal Si and the formation mechanism of primary crystal Si parcel eutectic structure by this growth mechanism.Li Quanbao etc.
[7]In order to obtain the component uniform HgCdTe crystals, the gravity separation of utilizing the HgCdTe melt under the hypergravity condition, to produce is offset the component fractional condensation that produces in the Bridgman process of growth.Liu Youzhi etc.
[8]With nano hydrated titanium oxide (TiO
2NH
2O) particle is the solid phase matrix, and Aluminum Chloride Hexahydrate solution is for coating phase, in rotary packed bed reactor drum at nano-TiO
2Particle surface has coated the fine and close spongy Al of one deck
2O
3Film.Mashimo T etc.
[9-10]Under the super gravity field effect, make the alloy material that Bi-Sb, In-Pb, Bi-Pb etc. have superstructure.Discovery owing to solute segregation produces the solute atoms deposition, is prepared the alloy material with laminate structure under the hypergravity effect, be expected to be used for fields such as superconduction.Huang XS etc.
[11-13]Discovery can promote the atomic diffusion deposition in the Bi-Sb alloy under the effect of superelevation gravity field, in the polycomponent condensed state, form compositional gradient structure or non-equilibrium phase.The above results shows that hypergravity is a kind of more extreme study condition, is expected to prepare the material with complex with non-equilibrium structure under such condition.
Hydrothermal method
[14,15]Be that a kind of single stage method prepares one of method of nano material.The nano material of many high temperature phases can directly make through this method, need not through sintering processes.But owing to carry out under the state of compeling non-receiving, the powder of formation has characteristics such as crystal grain complete crystallization, good dispersivity, is difficult to make metastable spherical powder by the nano-powder of Hydrothermal Preparation.In order to overcome above-mentioned shortcoming; The present invention combines to be prone under the hypergravity to make the characteristics that non-equilibrium material and hydro-thermal reaction technology can directly make nano material; Propose a kind of technology of preparing---supergravity hydrothermal reaction technology of new spherical powder particle, and adopt this technology successfully to prepare various spheric inorganic powder grains.
Reference
[1] Hu Xiaoyun, Zheng Mingbo, Zhao Yanfei, Liu Jingsong, plum is complete, and Cao Jieming utilizes colloidal carbon sphere to prepare SiO for template
2, TiO
2, SnO
2Hollow ball chemical research and application, 18 (4): 415-418 (2006).
[2] Wang Hongyi, Liao Xuehong, the preparation of tiny balloon structured material and application, micro-nano electronic technology, 10:470-475 (2006).
[3] Sun Ruixue, Li Musen, Lv Yupeng, the preparation of tiny balloon type material and progress of application, material Leader, 19 (10): 19-22 (2005).
[4] Kuang Yi, Guo Yanhua, the preparation of tiny balloon and progress of application, colloid and polymkeric substance, 25 (3): 41-43 (2007),
[5] how refined Xu Huarui is, is equipped with solid spherical cerium oxide ultrafine powder with the spray reaction legal system, rare earth, and 20 (6): 29-31 (1999),
[6] Wang Qudong, Jin Junze. the growth of centrifugal incline liquid method and primary crystal Si. the artificial lens journal, 1998,27 (1): 94-97,
[7] Li Quan preserves .HgCdTe hypergravity crystal growth system principle design. infrared technique, 1999,05.，
[8] Liu Youzhi, Guo Yu, Shi Guoliang, Dong Xiufang, Lee is abundant. and the nano TiO 2 particle surface coats Al in the super gravity field
2O
3Film and sign thereof. chemical industry progress, 2006,03.
[9]Mashimo?T.，Iguchi?Y.，Bagum?R.，Sano?T.，Sakata?O.，Ono?M.，Okayasu?S..Formation?ofmulti-layer?structures?in?Bi3Pb7?intermetallic?compounds?under?an?ultra-high?gravitational?field.AIP?Conference?Proceedings，2008，973：502-5.
[10]Ono?M.，Iguchi?Y.，Bagum?R.，Fujii?K.，Okayasu?S.，Esaka?F.，Mashimo?T..Ultracentrifugeexperiment?on?an?Mg-Cd?order-disorder?alloy.AIP?Conference?Proceedings，2008，973：476-81.
[11]Xinsheng?Huang，Mashimo?T.，Masao?Ono，Tomita?T.，Sawai?T.，Osakabe?T.，Mori?N..Effects?of?ultrastrong?gravitational?field?on?the?crystalline?state?of?a?bi-Sb?alloy.Journal?ofApplied?Physics，2004，96(3)：1336-40.
[12]Huang?X.S.，Mashimo?T.，Ono?M.，Tomita?T.，Sawai?T.，Osakabe?T.，Mori?N..Observation?ofcrystalline?state?of?the?graded?structure?Bi-Sb?alloy?prepared?under?a?strong?gravitational?field?ofaround?1?million?G.Advances?in?Space?Research.2003，32(2)：231-235.
[13]Xinsheng?Huang，Masao?Ono，Ueno?H.，Iguchi?Y.，Tomita?T.，Okayasu?S.，Mashimo?T..Formation?of?atomic-scale?graded?structure?in?Se-Te?semiconductor?under?strong?gravitationalfield.Journal?of?Applied?Physics，2007，101(11)：113502/1-5.
[14] Li Wenjun, Shi Er fear, Tian Mingyuan, the tall and erect .Synthesis of of Zhong Wei ZnO fibers and nanometer powders byhydrothermal method.Science in China, Ser.E, 1998,05.
[15]Lei?Ji-xia，Liu?Xiao-lin，Chen?Jian-feng..Hydrothermal?synthesis?and?structurecharacterization?of?nanocrystalline?barium?titanate?powders.Advanced?Materials?Research，2006，11-12：23-26.
Summary of the invention
The object of the invention is to provide a kind of supergravity hydrothermal preparation method of inorganic spherical powder particle.
The method that the present invention adopted is: be utilized in aqueous phase and add bigger than water, not miscible with water organic reagent or the density water-soluble polymer reagent bigger than water of density; The oil that under centrifugal action, in autoclave, forms/water heterogeneous system; Make under 50-250 ℃ temperature of reaction; The nucleus that aqueous phase forms in autoclave is in the centrifugal action deposit on oil/water termination or in the oil phase, and is self-assembled into spherical powder particle on oil/water termination or in the oil phase.Wherein the water in oil/water heterogeneous system is water-soluble liquid phase, oil phase be density bigger than water, not with the miscible organic solution of water mutually or the density water-soluble polymer phase bigger than water, precursor is dissolved in aqueous phase.
The overweight hydrothermal preparing process of measuring one's own ability of the inorganic spherical powder particle that the present invention proposes; The hydro-thermal reaction equipment that can produce hypergravity that is adopted comprises centrifugal device, autoclave and temperature-controlled oven, and centrifugal device comprises motor 9 and is installed in the fixed support 6 on the machine shaft 8; Temperature-controlled oven comprises temperature controller 11, heater strip 3, insulating brick 2, body of heater shell 1 and anti-riot tube 4; Be provided with anti-riot tube 4 around the burner hearth of temperature-controlled oven; The outer insulating brick 2 that is provided with of anti-riot tube, insulating brick 2 is outer to be body of heater shell 1, between the anti-riot tube 4 of both sides and insulating brick 2, is provided with heater strip 3; Autoclave 5 comprises kettle cover, kettle and polytetrafluoroethyllining lining; The fixed support 6 of centrifugal device stretches into from the bottom in the burner hearth of temperature-controlled oven, and autoclave 5 is installed on the fixed support 6 of centrifugal device; Body of heater outer casing bottom and machine shaft 8 both sides are respectively equipped with water-cooled tube 7; Temperature controller 11 connects a side of centrifugal device; Concrete steps are following:
(1) in deionized water, adds the metal-salt precursor, be mixed with the metal salt solution of concentration 0.001-2mol/L;
(2) adding can produce S accordingly under 50-250 ℃ temperature of reaction in the solution of step (1)
2-Chemical reagent, regulate the pH value and make its dissolving; Wherein, the mol ratio of ionizable metal salt and sulfonium ion is 1: 1-1: 5;
(3) in step (2) gained solution, add density than water big and water-fast organic solvent or the density water-soluble high-molecular compound bigger than water, wherein the volume ratio of organic solvent or water-soluble high-molecular compound and metal salt solution is: 1: 1-1: 50;
(4) step (3) blended solution is packed in the autoclave, be fixed on after the sealing on the fixed support in the burner hearth, in the presence of hypergravity, carry out hydro-thermal reaction at a certain temperature.Its temperature of reaction is: 50-250 ℃, the reaction times is: 0.1-5h, relative centrifugal force are 100 grams-10000 grams:
(5) step (4) products therefrom is filtered, and the solid product after will filtering cleans (being generally 3-6 time) repeatedly with dithiocarbonic anhydride, second alcohol and water, vacuum-drying promptly gets desired product.
Among the present invention, metal-salt precursor described in the step (1) is one or more the combination in muriate, nitrate salt, vitriol or the acetate of metal.
Among the present invention, produce S under 50-250 ℃ temperature of reaction, can decompose described in the step (2)
2-Chemical reagent be in Sulfothiorine, sulfo-hexanamide or the thiocarbamide etc. one or more.
Among the present invention, the described density of step (3) than big, the water-fast organic solvent of water be in tetracol phenixin, chloroform, dithiocarbonic anhydride, chlorobenzene, bromobenzene, phenylate, orthodichlorobenzene or the oil of mirbane etc. any; Said water-soluble high-molecular compound be in polyoxyethylene glycol or the polyoxyethylene etc. any.
Among the present invention, the volume ratio of described organic solvent of step (3) or water-soluble high-molecular compound and step (1) gained metal salt solution is 1: 1-1: 10.
Among the present invention, the relative centrifugal force of the generation hypergravity described in the step (4) is 500 grams-3000 grams.
Among the present invention, the vacuum-drying temperature is 30-100 ℃ described in the step (5), and the time is 1-4 hour.
Adopt technique scheme, beneficial effect of the present invention is: the inorganic spherical powder particle that (1) makes has the characteristics of high circularity, single dispersion, narrow distribution; (2) equipment is simple, and reaction is control easily, is easy to realize industriallization.The inorganic powder that utilizes the inventive method to make comprises: ZnS, CdS, CuS, PbS etc.The technological thus inorganic spherical powder particle that makes has characteristics such as high circularity, monodispersity, narrow distribution, can be used for making photonic crystal, rare earth luminescent material, phonon crystal, solar energy materials, LHM etc.
Description of drawings
Fig. 1 is a kind of supergravity hydrothermal conversion unit structural representation,
Fig. 2 is that embodiment 2 is with 0.1-1mol/L CdCl
2And Na
2S
2O
3For precursor carries out the SEM photo of the CdS powder that hydro-thermal reaction makes, wherein CdCl under hypergravity in oil of mirbane/water
2And Na
2S
2O
3Mol ratio be 1: 2.
Fig. 3 is that embodiment 3 is with 0.1-1mol/L ZnCl
2And Na
2S
2O
3For precursor carries out the SEM photo of the ZnS powder that hydro-thermal reaction makes, wherein ZnCl under hypergravity in phenylate/water
2And Na
2S
2O
3Mol ratio be 1: 1.
Fig. 4 is that embodiment 4 is with 0.1-1mol/L Pb (NO
3)
2With thiocarbamide be precursor carries out the PbS powder that hydro-thermal reaction makes under hypergravity in bromobenzene/water SEM photo, wherein Pb (NO
3)
2With the mol ratio of thiocarbamide be 1: 4.
Fig. 5 is embodiment 5 with 0.1-1mol/L manganese acetate and sulfo-hexanamide is precursor carries out the MnS powder that hydro-thermal reaction makes under hypergravity in oil of mirbane/water SEM photo, and wherein the mol ratio of manganese acetate and sulfo-hexanamide is 1: 2.
Fig. 6 is that embodiment 6 is with 0.1-1mol/L Co (SO
4)
2With thiocarbamide be precursor carries out the CoS powder that hydro-thermal reaction makes under hypergravity in dichlorobenzene/water SEM photo, wherein Co (SO
4)
2With the mol ratio of thiocarbamide be 1: 3.
Fig. 7 is that embodiment 7 is with 0.1-1mol/L NiCl
2With the sulfo-hexanamide be precursor carries out the NiS powder that hydro-thermal reaction makes under hypergravity in chlorobenzene/water SEM photo, wherein NiCl
2With the mol ratio of sulfo-hexanamide be 1: 1.
Label among the figure: 1 is the body of heater shell, and 2 is insulating brick, and 3 is heater strip, and 4 is anti-riot tube, and 5 is autoclave, and 6 is fixed support, and 7 is water-cooled tube, and 8 are rotating shaft, and 9 is motor, and 10 is fan blade, and 11 is temperature controller.
Embodiment
Below further specify process step and the condition that adopts the supergravity hydrothermal preparation method to prepare spherical powder particle through instance; But organic solvent is not limited to orthodichlorobenzene and polyoxyethylene glycol, all can use with the immiscible organic solvent tetracol phenixin of water, chloroform, dithiocarbonic anhydride, chlorobenzene, bromobenzene, phenylate, orthodichlorobenzene or oil of mirbane.
Fig. 1 is a kind of supergravity hydrothermal conversion unit structural representation, wherein: 1. body of heater shell, 2 insulating bricks, 3 heater strips, 4 anti-riot tubes, 5 autoclaves, 6 fixed supports, 7 water-cooled tubes, 8 rotating shafts, 9 motors, 10 fan blades, 11 do
The structure of equipment comprises centrifugal device, autoclave, temperature-controlled oven, and wherein centrifugal device comprises motor and is fixed on the fixed support on the machine shaft; Temperature-controlled oven comprises temperature controller, nichrome wire, lagging material and body of heater shell; Autoclave comprises kettle cover, kettle and polytetrafluoroethyllining lining.The fixed support of centrifugal device is positioned at the cavity of temperature-controlled oven, and autoclave is installed on the fixed support of centrifugal device.
The preparation of spherical Cadmium Sulfide particle powder: its preparation process is:
Step 1: in 5 milliliters deionized water, add a certain amount of Cadmium chloride fine powder, be made into the cadmium chloride solution that concentration is 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of thioacetamide, regulate pH value it is dissolved, and to require the mol ratio of Cadmium chloride fine powder and Sulfothiorine be 1: 2;
Step 3: in the solution of step 2, add 2 milliliters of bromobenzenes;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 1000 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 1h.Adopt sem that the pattern of sample is characterized.Fig. 2 is the SEM photo of the Cadmium Sulfide that makes by above step.The coating of particles that is as can beappreciated from fig. 2 made by above method is spherical, and particle size is about 1 micron.
The preparation of spherical zine sulfide particle powder: its preparation process is:
Step 1: in 5 milliliters deionized water, add a certain amount of zinc chloride, be made into the liquor zinci chloridi that concentration is 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of Sulfothiorine, regulate pH value it is dissolved, and to require the mol ratio of zinc chloride and sulfo-hexanamide be 1: 1;
Step 3: in the solution of step 2, add 1.5 milliliters of orthodichlorobenzenes;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 1500 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.
Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 2h.Adopt sem that the pattern of sample is characterized.Fig. 3 is the SEM photo of the zinc sulphide that makes by above step.The coating of particles that is as can beappreciated from fig. 3 made by above method is spherical, and particle size is about 200 nanometers.
The preparation of spherical lead sulfide particle powder: its preparation process is:
Step 1: in 10 milliliters deionized water, add a certain amount of lead nitrate, be made into the lead nitrate solution that concentration is 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of thiocarbamide, regulate pH value it is dissolved, and to require the mol ratio of lead nitrate and thiocarbamide be 1: 4;
Step 3: in the solution of step 2, add 1.5 milliliters of phenylates;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 2000 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.
Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 3h.Adopt sem that the pattern of sample is characterized.Fig. 4 is the SEM photo of the lead sulfide that makes by above step.The coating of particles that is as can beappreciated from fig. 4 made by above method is spherical, and particle size is about 100 nanometers.
The preparation of spherical manganese sulfide particle powder: its preparation process is:
Step 1: in 10 milliliters deionized water, add a certain amount of manganese acetate, being made into concentration is the manganese acetate solution of 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of sulfo-hexanamide, regulate pH value it is dissolved, and to require the mol ratio of manganese acetate and sulfo-hexanamide be 1: 2;
Step 3: in the solution of step 2, add 1 milliliter of oil of mirbane;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 3000 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.
Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 2h.Adopt sem that the pattern of sample is characterized.Fig. 5 is the SEM photo of the manganese sulfide that makes by above step.The coating of particles that is as can beappreciated from fig. 5 made by above method is spherical, and particle size is about 1.5 microns.
The preparation of spherical cobaltous sulfide particle powder: its preparation process is:
Step 1: in 20 milliliters deionized water, add a certain amount of rose vitriol, be made into the cobalt sulfate solution that concentration is 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of thiocarbamide, regulate pH value it is dissolved, and to require the mol ratio of rose vitriol and thiocarbamide be 1: 3;
Step 3: in the solution of step 2, add 1 milliliter of oil of mirbane;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 500 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.
Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 4h.Adopt sem that the pattern of sample is characterized.Fig. 6 is the SEM photo of the cobaltous sulfide that makes by above step.The coating of particles that is as can beappreciated from fig. 6 made by above method is spherical, and particle size is about 200 nanometers.
The preparation of spherical nickelous sulfide particle powder: its preparation process is:
Step 1: in 4 milliliters deionized water, add a certain amount of nickelous chloride, be made into the nickel chloride solution that concentration is 0.1-1mol/l;
Step 2: in the solution of step 1, add a certain amount of thiocarbamide, regulate pH value it is dissolved, and to require the mol ratio of nickelous chloride and thiocarbamide be 1: 1;
Step 3: in the solution of step 2, add 4 milliliters of oil of mirbane;
Step 4: pack the mixing solutions of step 3 in the autoclave into, the good seal autoclave, and be fixed on the fixed support in the hypergravity conversion unit shown in Figure 1.Making relative centrifugal force then is 2000 grams, and heat temperature raising is incubated half a hour to 120-150 ℃, the cooling cooling.
Take out product, with dithiocarbonic anhydride, ethanol and zero(ppm) water product is carried out repeatedly repetitive scrubbing respectively, then at 80 ℃ of vacuum-drying 3h.Adopt sem that the pattern of sample is characterized.Fig. 7 is the SEM photo of the nickelous sulfide that makes by above step.The coating of particles that is as can beappreciated from fig. 7 made by above method is spherical, and particle size is about 400 nanometers.
Claims (7)
1. the overweight hydrothermal preparing process of measuring one's own ability of an inorganic spherical powder particle; It is characterized in that the hydro-thermal reaction equipment that can produce hypergravity that is adopted comprises centrifugal device, autoclave and temperature-controlled oven, centrifugal device comprises motor (9) and is installed in the fixed support (6) on the machine shaft (8); Temperature-controlled oven comprises temperature controller (11), heater strip (3), insulating brick (2), body of heater shell (1) and anti-riot tube (4); Be provided with anti-riot tube (4) around the burner hearth of temperature-controlled oven; The outer insulating brick (2) that is provided with of anti-riot tube; Insulating brick (2) is outer to be body of heater shell (1), is positioned between anti-riot tube (4) and the insulating brick (2) of both sides to be provided with heater strip (3); Autoclave (5) comprises kettle cover, kettle and polytetrafluoroethyllining lining; The fixed support of centrifugal device (6) stretches into from the bottom in the burner hearth of temperature-controlled oven, and autoclave (5) is installed on the fixed support (6) of centrifugal device; Body of heater outer casing bottom and machine shaft (8) both sides are respectively equipped with water-cooled tube (7); Temperature controller (11) connects a side of centrifugal device; Concrete steps are following:
(1) in deionized water, adds the metal-salt precursor, be mixed with the metal salt solution of concentration 0.001-2mol/L;
(2) adding can produce S accordingly under 50-250 ℃ temperature of reaction in the solution of step (1)
2-Chemical reagent, regulate the pH value and make its dissolving; Wherein, the mol ratio of ionizable metal salt and sulfonium ion is 1: 1-1: 5;
(3) in step (2) gained solution, add density than water big and water-fast organic solvent or the density water-soluble high-molecular compound bigger than water, wherein the volume ratio of organic solvent or water-soluble high-molecular compound and metal salt solution is: 1: 1-1: 50;
(4) step (3) blended solution is packed in the autoclave; Be fixed on after the sealing on the fixed support in the burner hearth; In the presence of hypergravity, carry out hydro-thermal reaction at a certain temperature; Its temperature of reaction is: 50-250 ℃, the reaction times is: 0.1-5h, relative centrifugal force are 100 grams-10000 grams;
(5) step (4) products therefrom is filtered, and the solid product after will filtering cleans with dithiocarbonic anhydride, second alcohol and water repeatedly, vacuum-drying promptly gets desired product.
2. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1 is characterized in that metal-salt precursor described in the step (1) is one or more the combination in muriate, nitrate salt, vitriol or the acetate of metal.
3. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1 is characterized in that producing under 50-250 ℃ temperature of reaction, can decompose described in the step (2) S
2-Chemical reagent be in Sulfothiorine, sulfo-hexanamide or the thiocarbamide one or more.
4. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1, it is characterized in that the described density of step (3) than big, the water-fast organic solvent of water be in tetracol phenixin, chloroform, dithiocarbonic anhydride, chlorobenzene, bromobenzene, phenylate, orthodichlorobenzene or the oil of mirbane any; Said water-soluble high-molecular compound be in polyoxyethylene glycol or the polyoxyethylene any.
5. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1 is characterized in that the volume ratio of described organic solvent of step (3) or water-soluble high-molecular compound and step (1) gained metal salt solution is 1: 1-1: 10.
6. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1, the relative centrifugal force that it is characterized in that the generation hypergravity described in the step (4) are 500 grams-3000 grams.
7. the overweight hydrothermal preparing process of measuring one's own ability of inorganic spherical powder particle according to claim 1 is characterized in that the vacuum-drying temperature is 30-100 ℃ described in the step (5), and the time is 1-4 hour.
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| CN102145924B (en) * | 2011-04-28 | 2012-12-05 | 同济大学 | Method for preparing alkaline cobalt carbonate under hyper-gravity hydrothermal condition |
| CN102249230A (en) * | 2011-05-13 | 2011-11-23 | 同济大学 | Method for preparing carbonate thin film under super-gravitational and hydrothermal conditions |
| CN102583558B (en) * | 2012-03-07 | 2013-08-07 | 陕西科技大学 | Preparation method of spherical gamma-MnS microcrystal |
| CN104213399A (en) * | 2014-08-26 | 2014-12-17 | 上海应用技术学院 | High-refractive-index structure color fiber with self assembly of ZnS nano balls and preparation method of high-refractive-index structure color fiber with self assembly of ZnS nano balls |
| CN105016374B (en) * | 2015-08-14 | 2017-01-04 | 天津城建大学 | A kind of preparation method of hierarchy CuS micron ball |
| CN106495192B (en) * | 2016-11-14 | 2018-05-15 | 南华大学 | A kind of method for preparing the uniform hydrotalcite of particle diameter distribution |
| CN111303872B (en) * | 2018-12-12 | 2021-06-01 | 北京化工大学 | Hypergravity preparation method of lead sulfide quantum dots |
| CN110156066A (en) * | 2019-05-06 | 2019-08-23 | 上海应用技术大学 | A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy |
| CN114229902B (en) * | 2021-12-20 | 2023-09-15 | 中原工学院 | Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof |
| CN115724773A (en) * | 2022-12-05 | 2023-03-03 | 宁夏东吴农化股份有限公司 | Method for preparing superfine nitroguanidine by virtue of supergravity hydrolytic crystallization method |
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