CN100573756C - A kind of method for preparing hollow magnetic ball - Google Patents
A kind of method for preparing hollow magnetic ball Download PDFInfo
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- CN100573756C CN100573756C CNB2005100198649A CN200510019864A CN100573756C CN 100573756 C CN100573756 C CN 100573756C CN B2005100198649 A CNB2005100198649 A CN B2005100198649A CN 200510019864 A CN200510019864 A CN 200510019864A CN 100573756 C CN100573756 C CN 100573756C
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Abstract
The present invention is the preparation method of hollow magnetic ball.This method is: the polymer latex particle that is rich in carboxyl with the surface is a template, utilize acid alcohol to interact, the inorganic forerunner's particle that the surface is rich in oh group is coated on the template particles, forms polymer-inorganic precursors core-shell nano compound particle, obtains hollow magnetic ball through Overheating Treatment again.This method has material compatibility widely, also may be used for other monobasic, binary or polynary single preparation that disperses the inorganic hollow ball, also has easy and simple to handle, with short production cycle, working condition easily and be easy to advantage such as popularization.
Description
Technical field
The present invention relates to the preparation method of the preparation method's of hollow magnetic ball, particularly submicron-scale monodisperse magnetic hollow ball.
Background technology
The micelle template is adopted in the preparation of inorganic hollow ball usually, promptly the latex particle with submicron-scale is a template, by layer upon layer electrostatic self-assembly method, sol-gal process, sluggish precipitation etc., inorganic precursors is coated on the template particles, remove template particles by pyrolysis or dissolving then, obtain corresponding inorganic sub-micro hollow ball.The inorganic hollow ball of numerous species prepares by the method, as TiO
2, SiO
2Deng, but because the special difficulty of preparation, the preparation of the ferrite hollow ball of monodispersed submicron yardstick does not still have report at present, and the research relevant with the preparation of polydispersity ferrite hollow ball also is phoenix feathers and unicorn horns, likes once as Central China University of Science and Technology in 2004 that 69～72 pages of perfume (or spice) [doctorate paper] " research of cenosphere composite wave-suction material ", 2005 " silicate journal " 33 phases appointed flat articles, the Wang Qi of Wuhan University of Technology [doctorate paper] " preparation of ferrite tiny balloon and magnetic metal core-shell particles and performance study " etc. in 2004.Hence one can see that, the method for preparing at present the barium ferrite hollow ball is: (1) spray pyrolysis: with oxy-acetylene flame or plasma flame is thermal source, powder art or suspension with the corresponding ferrite predecessor of chemical coprecipitation preparation are ejectisome, collect the spray pyrolysis product and heat-treat.Adopt spray pyrolysis that two big defectives are arranged, the one, the structure of hollow ball can not get guarantee, the 2nd, the particle size distribution broad of product, particle diameter polydispersion.(2) at the sol-gal process on hollow glass micro-ball surface: after hollow glass micro-ball surface hydroxylation and activation, insert in the colloidal sol of barium ferrite predecessor and carry out gelation reaction.When utilizing the Prepared by Sol Gel Method barium ferrite hollow ball on hollow glass micro-ball surface, the barium ferrite predecessor be difficult to remove with the hollow glass micro-ball as template, and available hollow glass micro-ball itself is a micro-meter scale easily from cohesion mutually, have polydispersity, and lack of homogeneity.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method for preparing hollow magnetic ball is provided, and this method is suitable for preparing the monodisperse iron base hollow magnetic ball of hollow magnetic ball, particularly submicron-scale with the technology of its original creation.
The technical solution adopted for the present invention to solve the technical problems is: the sub-micro polymer latex particle that is rich in carboxyl with the surface is a template, utilize acid alcohol to interact, the inorganic forerunner's particle that the surface is rich in oh group is coated on the template particles, form polymer-inorganic precursors core-shell nano compound particle, obtain hollow magnetic ball through Overheating Treatment again.
Principle of the present invention is: this is a kind of compound based on the interactional core-shell particles of acid alcohol, because carboxyl has been rich on the template particles surface, and hydroxyl has been rich on the inorganic precursors surface that makes in polyglycol solution, adding along with inorganic precursors, acid alcohol takes place between template particles and the predecessor to interact, carboxylic acid composition in the template particles is consumed gradually as a result, correspondingly, inorganic precursors is covered by on the polymer latex particle gradually, thereby obtain corresponding nucleocapsid compound particle, handle through hollowization and mineralising, the nucleocapsid compound particle is transformed into corresponding hollow magnetic ball.
The present invention compared with prior art has following remarkable result:
One. with the polymer latex particle is template, and preparation polymer-inorganic matter core-shell nano compound particle again with the pyrolysis of polymer template latex particle, obtains corresponding inorganic hollow ball.The particle size distribution of hollow ball and interior nuclear diameter depend on the particle size distribution and the size of polymer template latex particle respectively, and the control of the particle size distribution of polymer template latex particle and size is relatively easy, as gathering (styrene-be total to-acrylic acid) latex particle with the synthetic single dispersion of the method for emulsifier-free emulsion polymerization, its size and surface texture thereof are easy to hold by experiment conditions such as the monomer concentration in the debugging polymerization system, initiator concentration, electrolyte concentrations.
They are two years old. and utilize the surface to be rich in the inorganic precursors of hydroxyl as chemical assembly element.Because chemical assembly element is based on the acid alcohol interaction principle and is coated on the polymer template latex particle and forms the nucleocapsid compound particle, therefore the present invention has material compatibility widely, also may be used for other monobasic, binary or polynary single preparation that disperses the inorganic hollow ball.
They are three years old. and easy and simple to handle, with short production cycle, working condition is easy, is easy to promote.
Embodiment
The invention provides a kind of be suitable for preparing hollow magnetic ball, the especially method of monodispersity submicron-scale hollow magnetic ball, its polymer latex particle that is rich in carboxyl with the surface is a template, utilize acid alcohol to interact, the inorganic forerunner's particle that the surface is rich in oh group is coated on the template particles, form polymer-inorganic precursors core-shell nano compound particle, obtain hollow magnetic ball through Overheating Treatment again.Concrete steps are as follows:
(1) synthetic polymer template latex particle: water, the hydrophilic monomer that contains carboxylic group or amphipathic monomer, hydrophobic monomer etc. are added in the flask, start stirring, heat up behind the displacement nitrogen, after rising to 50～100 ℃, temperature dropwise adds initator, and be incubated 15～36 hours, and being cooled to room temperature at last, synthetic polymer template latex particle is after eccentric cleaning repeatedly, again be dispersed in the water, make mass fraction and be 1% polymer emulsion.
The polymer template latex particle is rich in the micron of carboxyl or the polymer latex particle of submicron-scale for the surface.
(2) inorganic precursors of hydroxyl is rich on preparation surface: water miscible iron group metal inorganic salts or water miscible iron group metal inorganic salts and water miscible other family's metal inorganic salt are dissolved in the polyethylene glycol aqueous solution, drip the co-precipitation agent, inorganic precursors is precipitated, through separating and purifying, obtain the inorganic precursors that hydroxyl is rich on the surface again.
Above-mentioned inorganic precursors is the mixed precursor of iron group metal inorganic salts or iron group metal inorganic salts and other family's metal inorganic salt composition, and the mol ratio of iron group metal inorganic salts and other family's metal inorganic salt is 1: 1～1: 30.Other family's metal inorganic salt is the inorganic salts of metals such as lithium, barium, strontium, magnesium, titanium, niobium, manganese, cobalt, nickel, zinc, aluminium.
(3) preparation core-shell nano compound particle: the inorganic precursors solution that is rich in hydroxyl by proper proportion mixing ready polymer emulsion of abovementioned steps (1) and the ready surface of abovementioned steps (2), and the pH value of control mixed system, by centrifugal or filter to isolate product, this product is the core-shell nano compound particle subsequently.
(4) hollowization and mineralising are handled: after the vacuumize of core-shell nano compound particle, insert in the high-temperature atmosphere furnace and heat-treat, heat treatment temperature is 300～1400 ℃, obtains end-product with the stove cooling afterwards, promptly obtains hollow magnetic ball.
Above-mentioned heat-treating methods is: earlier at N
2Or under the air atmosphere, be warmed up to 300～500 ℃ from room temperature with certain heating rate, be incubated and be adjusted into H after 0.3～4.0 hour
2Or O
2Reducing atmosphere, and continue insulation 0.5～24 hour, being warmed up to 500～1400 ℃ with certain heating rate again, and being incubated 0.5～24 hour, certain heating rate is 0～20 ℃/min, obtains hollow magnetic ball with the stove cooling then.
Below in conjunction with specific embodiment the present invention is further described.
Specific embodiment
Embodiment 1:
1. nuclear diameter is that 150nm, shell thickness are single barium ferrite magnetic hollow ball that disperses of 10nm in the preparation.
2. equipment: the 500mL round-bottomed flask, electric mixer, heating collar, the 50mL crucible, maximum operating temperature is 1600 ℃ a high-temperature atmosphere furnace.
3. preparation process:
(1) synthetic single poly-(styrene-be total to-acrylic acid) sub-micro template latex particle that disperses: successively 300mL water, 30mL styrene, 10mL acrylic acid, 0.05g sodium chloride are added in the flask, start stirring, heat up behind the displacement nitrogen, rise in temperature that dropwise to add the 20mL mass fraction after 60 ℃ be 3% persulfate aqueous solution, and be incubated 24 hours, be cooled to room temperature at last, eccentric cleaning is distributed to poly-(styrene-altogether-acrylic acid) emulsion that is made into 2%wt in the water after repeatedly.
(2) the polyethylene glycol aqueous solution of preparation barium nitrate and ferric nitrate, wherein [Ba
2+]=0.010mol/L, [Fe
3+]=0.110mol/L, [PEG1000]/[NO
3 -]=20; At normal temperatures above-mentioned drips of solution is added in isopyknic 0.50mol/L NaOH aqueous solution, stir while dripping, dropwise continue to stir after 30 minutes that product is centrifugal, topple over and liquid, again with water clean repeatedly, centrifugal, and be dispersed in the water again make～suspension of 0.5% mass concentration is standby.
(3) preparation core-shell nano compound particle: the barium ferrite predecessor suspension of～0.5% concentration slowly joined while stirring in 1.0% P (St-co-AA) emulsion, reach 7.0 until the pH of emulsion value, add the back that finishes and continue to stir 30min, obtain P (St-co-AA)-barium ferrite predecessor core-shell particles, core-shell particles is through eccentric cleaning repeatedly.
(4) hollowization and mineralising are handled: will, be inserted in the high-temperature atmosphere furnace and heat-treat after 20 hours 60 ℃ of vacuumizes by the core-shell nano compound particle that abovementioned steps (3) obtain, heat treating regime be: earlier at N
2Speed with 4 ℃/min under the atmosphere is warmed up to 400 ℃ from room temperature, is adjusted into O behind the insulation 1hr
2Atmosphere, and continue insulation 3hr, the speed with 2 ℃/min is warmed up to 750 ℃ then, and insulation 2hr, cools off with stove afterwards.
Nuclear diameter is that 150nm, shell thickness are single barium ferrite magnetic hollow ball that disperses of 10nm in finally obtaining.
Embodiment 2:
1. nuclear diameter is that 300nm, shell thickness are the single dispersion metal ferromagnetism hollow ball of 15nm in the preparation.
2. equipment: with embodiment 1.
3. preparation process:
(1) synthetic single poly-(styrene-be total to-acrylic acid) sub-micro template latex particle that disperses: successively 300mL water, 30mL styrene, 10mL acrylic acid, 0.05g sodium chloride are added in the flask, start stirring, heat up behind the displacement nitrogen, rise in temperature that dropwise to add the 10mL mass fraction after 60 ℃ be 3% persulfate aqueous solution, and be incubated 24 hours, be cooled to room temperature at last, eccentric cleaning is distributed to poly-(styrene-altogether-acrylic acid) emulsion that is made into 2%wt in the water after repeatedly.
(2) the polyethylene glycol aqueous solution of preparation ferric nitrate, wherein [Fe
3+]=0.10mol/L, [PEG1000]/[NO
3 -]=30; At normal temperatures above-mentioned drips of solution is added in isopyknic 0.30mol/L NaOH aqueous solution, stir while dripping, dropwise continue to stir after 30 minutes that product is centrifugal, topple over and liquid, again with water clean repeatedly, centrifugal, and be dispersed in the water again make～suspension of 0.5% mass concentration is standby.
(3) preparation core-shell nano compound particle: the suspension of above-mentioned～0.5% concentration slowly joined while stirring in 1.0% P (St-co-AA) emulsion, reach 7.0 until the pH of emulsion value, add the back that finishes and continue to stir 30min, obtain P (St-co-AA)/barium ferrite predecessor core-shell particles, core-shell particles is through eccentric cleaning repeatedly.
(4) hollowization and mineralising are handled: will, be inserted in the high-temperature atmosphere furnace and heat-treat after 20 hours 60 ℃ of vacuumizes by the core-shell nano compound particle that abovementioned steps (3) obtain, heat treating regime be: earlier at O
2Or the speed with 4 ℃/min is warmed up to 450 ℃ from room temperature under the air atmosphere, is adjusted into H behind the insulation 3hr
2Atmosphere, and continue insulation 1hr, cool off with stove afterwards.
Nuclear diameter is that 150nm, shell thickness are the single dispersion metal ferromagnetism hollow ball of 10nm in finally obtaining.
Embodiment 3:
1. nuclear diameter is that 300nm, shell thickness are single spinel-type hollow magnetic ball that disperses of 30nm in the preparation.
2. equipment: with embodiment 1.
3. preparation process:
(1) with embodiment 1.
(2) the polyethylene glycol aqueous solution of preparation ferric nitrate and nickel nitrate, wherein [N
i 2+]=0.010mol/L, [Fe
3+]=0.020mol/L, [PEG6000]/[NO
3 -]=25; Above-mentioned drips of solution is added in isopyknic 0.20mol/LNaOH aqueous solution at normal temperatures, stir while dripping, dropwise continue to stir after 30 minutes that product is centrifugal, topple over and liquid, again with water clean repeatedly, centrifugal, and be dispersed in the water again make～suspension of 0.3% mass concentration is standby.
(3) preparation core-shell nano compound particle: the Ni ferrite predecessor suspension of above-mentioned～0.3% concentration slowly joined while stirring in 1.0% P (St-co-AA) emulsion, reach 7.0 until the pH of emulsion value, add the back that finishes and continue to stir 30min, obtain P (St-co-AA)-Ni ferrite predecessor core-shell particles, core-shell particles is through eccentric cleaning repeatedly.
(4) hollowization and mineralising are handled: will, be inserted in the high-temperature atmosphere furnace and heat-treat after 20 hours 60 ℃ of vacuumizes by the core-shell nano compound particle that abovementioned steps (3) obtain, heat treating regime be: earlier at N
2Speed with 4 ℃/min under the atmosphere is warmed up to 400 ℃ from room temperature, is adjusted into O behind the insulation 1hr
2Atmosphere, and continue insulation 3hr, the speed with 2 ℃/min is warmed up to 850 ℃ then, and insulation 2hr, cools off with stove afterwards.
Nuclear diameter is that 300nm, shell thickness are single spinel-type hollow magnetic ball that disperses of 30nm in finally obtaining.
Claims (5)
1. method for preparing hollow magnetic ball, the polymer latex particle that it is characterized in that being rich in the surface carboxyl is a template, utilize acid alcohol to interact, the inorganic forerunner's particle that the surface is rich in oh group is coated on the template particles, form polymer-inorganic precursors core-shell nano compound particle, obtain hollow magnetic ball through Overheating Treatment again.
2. the method for preparing hollow magnetic ball according to claim 1 is characterized in that hollow magnetic ball is made by following steps:
(1) synthetic polymer template latex particle: water, the hydrophilic monomer that contains carboxylic group or amphipathic monomer, hydrophobic monomer are added in the flask, start stirring, heat up behind the displacement nitrogen, after temperature rises to 50～100 ℃, dropwise add initator, and be incubated 15～36 hours, be cooled to room temperature at last, synthetic polymer template latex particle is after eccentric cleaning repeatedly, in water, disperse again, make certain density polymer emulsion
The polymer template latex particle is rich in the micron of carboxyl or the polymer latex particle of submicron-scale for the surface,
(2) inorganic precursors of hydroxyl is rich on preparation surface: water miscible iron group metal inorganic salts or water miscible iron group metal inorganic salts and water miscible other family's metal inorganic salt are dissolved in the polyethylene glycol aqueous solution, drip the co-precipitation agent, inorganic precursors is precipitated, again through separating and purifying, obtain the surface and be rich in the inorganic precursors of hydroxyl
Other family's metal inorganic salt is the inorganic salts of lithium, barium, strontium, magnesium, titanium, niobium, manganese, cobalt, nickel, zinc, aluminum metal,
(3) preparation core-shell nano compound particle: the inorganic precursors that polymer emulsion and surface is rich in hydroxyl is mixed, and the pH value of control mixed system, and by centrifugal or filter to isolate product, this product is the core-shell nano compound particle subsequently,
(4) hollowization and mineralising are handled: after the vacuumize of core-shell nano compound particle, insert in the high-temperature atmosphere furnace and heat-treat, heat treatment temperature is 300～1400 ℃, obtains end-product with the stove cooling afterwards, promptly obtains hollow magnetic ball.
3. the method for preparing hollow magnetic ball according to claim 2, it is characterized in that: the inorganic precursors that hydroxyl is rich on the surface is the mixed precursor of iron group metal inorganic salts or iron group metal inorganic salts and other family's metal inorganic salt composition, and the iron group metal inorganic salts in the described mixed precursor and the mol ratio of other family's metal inorganic salt are 1: 1～1: 30.
4. the method for preparing hollow magnetic ball according to claim 2 is characterized in that to the core-shell nano compound particle method of heat-treating being: earlier at N
2Or under the air atmosphere, be warmed up to 300～500 ℃ from room temperature with certain heating rate, be incubated and be adjusted into H after 0.3～4.0 hour
2Or O
2Reducing atmosphere, and continue insulation 0.5～24 hour is warmed up to 500～1400 ℃ with certain heating rate again, and is incubated 0.5～24 hour, certain heating rate be greater than 0 ℃/min smaller or equal to 20 ℃/min, cool off with stove then and obtain hollow magnetic ball.
5. according to claim 2 or the 4 described methods that prepare hollow magnetic ball, it is characterized in that: hollow magnetic ball is the iron-based hollow magnetic ball of micron or submicron-scale.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110132144A1 (en) * | 2008-07-23 | 2011-06-09 | Jochen Mezger | Method For Producing Metal Nanoparticles In Polyols |
| CN101552064B (en) * | 2008-12-16 | 2011-01-26 | 北京理工大学 | Method for preparing hollow magnetic ball |
| CN101898749B (en) * | 2010-08-02 | 2014-07-02 | 武汉理工大学 | Method for preparing metal oxide hollow particles or fibers |
| CN102938459B (en) * | 2012-11-14 | 2015-09-30 | 浙江南都电源动力股份有限公司 | A kind of method preparing positive material of high-power lithium ion battery |
| CN103100360B (en) * | 2012-12-30 | 2015-04-01 | 杭州师范大学 | Preparation method of hollow inorganic submicron particle |
| CN104276606B (en) * | 2014-07-30 | 2016-01-20 | 安顺学院 | Silicon magnetic hollow ball ZnSi xfe 2-xo 4preparation method, application and renovation process |
| CN106444099B (en) * | 2016-12-20 | 2019-02-05 | 武汉理工大学 | Can magneto discoloration auto-orientation photonic crystal ball and preparation method thereof |
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