CN1290648C - Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same - Google Patents
Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same Download PDFInfo
- Publication number
- CN1290648C CN1290648C CN200410041128.9A CN200410041128A CN1290648C CN 1290648 C CN1290648 C CN 1290648C CN 200410041128 A CN200410041128 A CN 200410041128A CN 1290648 C CN1290648 C CN 1290648C
- Authority
- CN
- China
- Prior art keywords
- core
- shell structure
- sio
- shell
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 10
- 239000002105 nanoparticle Substances 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052681 coesite Inorganic materials 0.000 title abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 2
- 239000000377 silicon dioxide Substances 0.000 title abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 2
- 229910052682 stishovite Inorganic materials 0.000 title abstract 2
- 229910052905 tridymite Inorganic materials 0.000 title abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000005416 organic matter Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- VYMHFSZGDLIMMG-UHFFFAOYSA-K iron(3+);diacetate;hydroxide Chemical compound [OH-].[Fe+3].CC([O-])=O.CC([O-])=O VYMHFSZGDLIMMG-UHFFFAOYSA-K 0.000 claims description 3
- -1 nitroso triacetic acid Chemical compound 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005373 pervaporation Methods 0.000 claims 1
- 230000005291 magnetic effect Effects 0.000 abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 230000008020 evaporation Effects 0.000 abstract description 9
- 230000005415 magnetization Effects 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
- Compounds Of Iron (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
具有核/壳结构的高稳定性Fe/SiO2复合纳米颗粒，是以纳米铁颗粒为核心，表面包覆SiO2壳层组成的具有核/壳结构的复合纳米颗粒。其制备方法是以铁盐为原料，有机酸为络合剂，无水乙醇或异丙醇为溶剂形成均匀非水溶胶，加入正硅酸乙脂，经过蒸发脱水形成凝胶，空气中预焙烧去除有机物，在H2气氛中不同温度下还原即得到小于10纳米具有核/壳结构的高稳定性Fe/SiO2复合纳米颗粒。本发明采用非水溶剂，不经过过滤洗涤步骤，因此SiO2壳层的厚度可以在很宽的范围内任意调整。制备工艺简单、过程容易控制，适宜大规模生产。产品的粒径小于10纳米，铁核心小于超顺磁临界尺寸，具有饱和磁化强度高、矫顽力低的优良的软磁性能。High stability Fe/SiO 2 composite nanoparticles with a core/shell structure is a composite nanoparticle with a core/shell structure composed of nano-iron particles as the core and a SiO 2 shell layer on the surface. Its preparation method is to use iron salt as raw material, organic acid as complexing agent, absolute ethanol or isopropanol as solvent to form a uniform non-aqueous sol, add ethyl orthosilicate, form gel after evaporation and dehydration, and pre-roast in the air Removal of organic matter and reduction at different temperatures in an H 2 atmosphere yields highly stable Fe/SiO 2 composite nanoparticles smaller than 10 nanometers and having a core/shell structure. The present invention uses a non-aqueous solvent without filtering and washing steps, so the thickness of the SiO2 shell can be adjusted arbitrarily within a wide range. The preparation process is simple, the process is easy to control, and is suitable for large-scale production. The particle size of the product is less than 10 nanometers, the iron core is smaller than the superparamagnetic critical size, and has excellent soft magnetic properties with high saturation magnetization and low coercive force.
Description
Technical field
The present invention relates to a kind of Fe/SiO with core/shell structure, high magnetic intensity, high stability
2Composite nanometer particle and preparation method thereof.Especially particle diameter is less than 10 nanometer Fe/SiO
2Composite nanometer particle and preparation method thereof.
Background technology
Ferrous metal is a magnetic moment maximum in the magnetic transition elements.The ferrous metal nanometer is made iron nano-particle have characteristics such as quantum size effect, small-size effect, skin effect, thereby show the character of many uniquenesses, have broad application prospects at aspects such as catalysis, photoelectricity, medicine, magnetizing mediums, high performance magnetic liquid.The preparation of relevant iron nano-particle and the research of character have caused people's extensive interest.But the transition metal of nano-scale is very easy to oxidation even spontaneous combustion at ambient temperature in air, has seriously hindered the practical application process of iron nano-particle.The preparation iron nano-particle generally all is (less than 10 in vacuum at present
-6Pa) or in inert gases such as the argon of low pressure, helium carry out, preparation process is loaded down with trivial details, equipment require high, be not suitable for large-scale production.We once adopted the nano-level iron oxide surface coated Si O for preparing at chemical coprecipitation
2The protective layer method of high temperature reduction is then prepared surperficial coated Si O
2The iron particle, preparation technology is simple, product stability height (patent applied for, application number 03132104.6), product cut size is distributed as the 50-200 nanometer.
Summary of the invention
The objective of the invention is to seek a kind of new preparation method, prepare particle diameter, have the Fe/SiO of core/shell structure, high magnetic intensity, high stability less than 10 nanometers
2Composite nanometer particle.Surperficial coated Si O in Armco magnetic iron nanometer core
2Shell effectively stops the oxidation of iron particle, increases substantially the stability of iron nano-particle, reduces the sintering in the heat treatment process simultaneously, suppresses growing up of crystallite dimension.The particle diameter of product is less than 10 nanometers, and the iron core is less than super paramagnetic critical dimension, has saturation magnetization height, good soft magnet performance that coercivity is low.A process for preparing next product because surperficial coated Si O
2The insulation shell, resistivity significantly improves, and can reduce eddy-current loss, thereby can significantly improve the high frequency characteristics of product.The present invention adopts nonaqueous solvents, without the filtration washing step, so SiO
2The thickness of shell can be adjusted arbitrarily in very wide scope.Preparation technology is simple, process is controlled suitable for mass production easily.
Technical scheme of the present invention is: be to be raw material with the molysite, organic acid is a complexing agent, and absolute ethyl alcohol or isopropyl alcohol are that solvent forms even colloidal sol (non-aqueous sol), adds tetraethoxysilance, forms gel through dehydration by evaporation, and organic matter is removed in preroast in the air, at H
2In the atmosphere under the different temperatures reduction promptly obtain having the high-stability Fc/SiO of core/shell structure less than 10 nanometers (general 5-10 nanometer)
2Composite nanometer particle.Molysite and organic acid mol ratio are 1: 1.0～1: 3.0; The complex reaction temperature is preferably above room temperature, especially is 50-80 ℃, reaction time 4-10 hour; Tetraethoxysilance is as SiO
2The silicon source of shell, SiO
2Covering amount be 1-30% (weight ratio); The dehydration by evaporation temperature is 70-90 ℃; Xerogel calcined temperature in air is 400-500 ℃, roasting time 4-10 hour; Reduction temperature is 500-900 ℃ in hydrogen, and the recovery time is 3-10 hour.With the iron particle of method preparation of the present invention, particle diameter is evenly distributed, and is generally the 5-8 nanometer, is no more than 10 nanometers, saturation magnetization 150-190Am
2/ kg, coercivity is less than 20kA/m.Fierce oxidation promptly takes place under the air at room temperature condition the simple iron particle of particle diameter 10 nanometers sends out the production of spontaneous combustion rapidly ferriferous oxide, that is to say the iron particle that can't obtain under normal condition less than 10 nanometers, let alone practical application.And the particle diameter of the present invention's preparation has the Fe/SiO of core/shell structure less than 10 nanometers
2Composite nanometer particle can long-term stability be present in the air under up to 150 ℃ of temperature.
Molysite commonly used is frerrous chloride, ferric trichloride, ferric nitrate, ferric sulfate etc., also can use the organic acid molysite, as basic ferric acetate, praseodynium iron etc.Complexing agent except that citric acid, also can use NTA (nitroso triacetic acid), HEDTA (N-HEDTA), EDTA (ethylenediamine tetra-acetic acid) etc. can with the organic acid of iron complexing.
Product with the present invention preparation carries out structure and performance characterization by following means: the thing that the D/Max-RA rotary anode X-ray diffractometer (XRD) that adopts Japanese Rigaku company to produce is determined magnetic nanometer particles mutually; The shape and size that the JEM-200CX transmission electron microscope (TEM) that utilizes Japanese JEOL company to produce is directly observed product; The magnetic property of product adopts the U.S. to produce LakeShore vibrating specimen magnetometer (VSM) and measures; The antioxygenic property of product adopts the comprehensive thermal analyzer of NETZSCH STA 449C to determine.The magnetic spectrum performance of product is measured by Agilent4284A (frequency range 20Hz is to 1MHz) and Agilent4191B (frequency range 1MHz is to 1.8GHz) electric impedance analyzer.
The present invention adopts nonaqueous solvents, without the filtration washing step, so SiO
2The thickness of shell can be adjusted arbitrarily in very wide scope.Preparation technology is simple, process is controlled suitable for mass production easily.A process for preparing next product because surperficial coated Si O
2The insulation shell, resistivity significantly improves, and can reduce eddy-current loss, thereby can significantly improve the high frequency characteristics of product.The composite nanometer particle particle diameter of preparing in addition can be used for preparing high performance magnetic liquid less than 10 nanometers.
Description of drawings
Fig. 1 is a magnetic spectrum survey map of the present invention, and curve a is the product of embodiment 1 preparation, and curve c is the product of embodiment 2 preparations, and curve b is that reduction temperature is the magnetic spectrum measurement result of 800 ℃ of products that make among the embodiment 3.
Fig. 2 is in the embodiment of the invention 3 preparation process, and the XRD spectra of the product that obtains under the different reduction temperatures in hydrogen atmosphere has six spectral lines.Illustrate that when reduction temperature is higher than 500 ℃ product is single cube α-Fe phase.Reduction temperature is respectively: No. 0 spectral line: 400 ℃; No. 1 spectral line: 500 ℃; No. 2 spectral lines: 600 ℃; No. 3 spectral lines: 700 ℃; No. 4 spectral lines: 800 ℃; No. 5 spectral lines: 900 ℃.
Fig. 3 is in the embodiment of the invention 3 preparation process, the TEM photo of the product that in hydrogen atmosphere, obtains under the different reduction temperatures, and instruction card bread covers SiO
2Shell can effectively reduce the sintering of particle in the heat treatment process, suppresses growing up of crystallite dimension, and reduction temperature is little to the influence of product cut size.The corresponding different photo of different reduction temperatures, reduction temperature is respectively: photo 1:500 ℃; Photo 2:600 ℃; Photo 3:700 ℃; Photo 4:800 ℃; Photo 5:900 ℃.
Fig. 4 is the magnetic property of product of the embodiment of the invention 3 preparation and the relation curve of reduction temperature, and the result shows the intensity of magnetization maximum (183Am of product when reduction temperature is 800 ℃
2/ kg), coercivity minimum (4kA/m) has best soft magnet performance.
Fig. 5 is in the embodiment of the invention 3 preparation process, the aerial thermogravimetric curve of the product that obtains under the different reduction temperatures, and the result shows that reduction temperature is high more, the product heat endurance is high more.Reduction temperature is respectively: No. 1 curve: 500 ℃; No. 2 curves: 600 ℃; No. 3 curves: 700 ℃; No. 4 curves: 800 ℃; No. 5 curves: 900 ℃.
The specific embodiment
Below be embodiments of the invention (agents useful for same is a chemical pure among the embodiment).
Embodiment 1: under the strong mixing, with 0.01mol FeCl
24H
2O and 0.015mol citric acid are dissolved in the 100mL absolute ethyl alcohol, and 60 ℃ continue to stir 6 hours, form homogeneous transparent colloidal sol; Add the 0.083mL tetraethoxysilance, 80 ℃ of dehydration by evaporation are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air places 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then.The product that obtains is about average grain diameter 5 nanometers, is to have amorphous Si O
2Shell, core are the composite nanometer particle of the a-Fe of cube crystalline phase, saturation magnetization 197Am
2/ kg, coercivity 2.6kA/m.The magnetic spectrum measurement result of product shows in frequency up to 10
8Before the Hz, μ ' is stabilized in 16, and μ " very low.The magnetic spectrum measurement result is seen Fig. 1 curve a.
Use ferric trichloride, ferric nitrate to obtain result similar to the above.
Embodiment 2: under the strong mixing, with 0.01mol FeCl
24H
2O and 0.015mol citric acid are dissolved in the 100mL absolute ethyl alcohol, and 60 ℃ continue to stir 6 hours, form homogeneous transparent colloidal sol; Add the 0.34mL tetraethoxysilance, 80 ℃ of dehydration by evaporation are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air places 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then.The product that obtains is about average grain diameter 5 nanometers, is to have amorphous Si O
2Shell, core are the composite nanometer particle of the α-Fe of cube crystalline phase, saturation magnetization 168Am
2/ kg, coercivity 3.8kA/m.The magnetic spectrum measurement result of product shows that μ ' basic maintenance in whole measuring frequency scope is constant, loss μ " very low, almost level off to 0.The magnetic spectrum measurement result is seen Fig. 1 curve c.
Embodiment 3: under the strong mixing, with 0.01mol FeCl
24H
2O and 0.015mol citric acid are dissolved in the 100mL absolute ethyl alcohol, and 60 ℃ continue to stir 6 hours ,-formation homogeneous transparent colloidal sol; Add the 0.167mL tetraethoxysilance, 75-80 ℃ of dehydration by evaporation is until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air placed under the tube furnace hydrogen atmosphere different temperatures (400-800 ℃) reduction 4 hours then.During 400 ℃ of reduction temperatures, contain the Fe that are not reduced in a large number in the products therefrom
3O
4Reduction temperature is at the product that obtains more than 500 ℃ has amorphous Si O
2Shell, core are the composite nanometer particle of the α-Fe of cube crystalline phase, and different reduction temperatures are handled the XRD spectra of the sample that obtains and seen Fig. 2; Reduction temperature is little to the influence of product cut size, and the TEM photo is seen Fig. 3; The magnetic property difference of the product that obtains under the different reduction temperatures, magnetic measurement results is seen Fig. 4; The aerial heat endurance of product that obtains under the different reduction temperatures is also inequality, and reduction temperature is high more, and the product heat endurance is good more, and the aerial thermogravimetric curve of product is seen Fig. 5; Intensity of magnetization maximum (183Am in the time of 800 ℃
2/ kg), coercivity minimum (4.0kA/m) has best soft magnet performance, and its magnetic spectrum measurement result shows μ ' basic constant (about 10), loss μ of keeping in whole measuring frequency scope " very low, almost level off to 0.The magnetic spectrum measurement result is seen Fig. 1 curve b.
Embodiment 4: under the strong mixing, with 0.01mol FeCl
36H
2O and 0.020mol citric acid are dissolved in the 100mL absolute ethyl alcohol, and 65 ℃ continue to stir 5 hours, form homogeneous transparent colloidal sol; Add the 0.17mL tetraethoxysilance, 80 ℃ of dehydration by evaporation are until generating xerogel; Xerogel 450 ℃ of preroast 4 hours in air places 750 ℃ of reduction of tube furnace hydrogen atmosphere 5 hours then.The product that obtains be average grain diameter less than 10 nanometers about, be to have amorphous Si O
2Shell, core are the composite nanometer particle of the α-Fe of cube crystalline phase, saturation magnetization 176Am
2/ kg, coercivity 3.6kA/m.Product was placed three months under the air at room temperature environment, and structure and magnetic property do not have any significant change.
Embodiment 5: under the strong mixing, with 0.01mol FeCl
24H
2O and 0.015mol NTA (nitroso triacetic acid) are dissolved in the 100mL absolute ethyl alcohol, and 65 ℃ continue to stir 5 hours, form homogeneous transparent colloidal sol; Add the 0.35mL tetraethoxysilance, 75 ℃ of dehydration by evaporation are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air places 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then.The product that obtains is about average grain diameter 5 nanometers, is to have amorphous Si O
2Shell, core are the composite nanometer particle of the α-Fe of cube crystalline phase.
Complexing agent can use HEDTA (N-HEDTA) to obtain identical result.
Embodiment 6: praseodynium iron is raw material, and citric acid is that complexing agent is dissolved in the 100mL isopropyl alcohol, and 650 ℃ continue to stir 5 hours, form homogeneous transparent colloidal sol; Add the 0.2mL tetraethoxysilance, 80-85 ℃ of dehydration by evaporation is until generating xerogel; Xerogel in air 450-500 ℃ preroast 3-4 hour, place 750-800 ℃ of tube furnace hydrogen atmosphere reduction 3-4 hour then.The product that obtains be average grain diameter less than 10 nanometers, be to have amorphous Si O
2Shell, core are the composite nanometer particle of the α-Fe of cube crystalline phase.The magnetic spectrum measurement result of product shows that μ ' basic maintenance in whole measuring frequency scope is constant, loss μ " very low, almost level off to 0.Be better than embodiment 1 on the performance.
The variation of embodiment 7, process conditions: under the condition of embodiment 6, use basic ferric acetate, citric acid is that complexing agent is dissolved in the 100mL isopropyl alcohol, xerogel calcined temperature in air is 400-450 ℃, roasting time 9-10 hour, reduction temperature is 500-600 ℃ in hydrogen, and the recovery time is 9-10 hour, result and 6 no significant differences.
Claims (2)
1, the high-stability Fc/SiO that has core/shell structure
2Composite nanometer particle is characterized in that with the nano iron particles being core, surperficial coated Si O
2The composite nanometer particle that shell is formed with core/shell structure, the average grain diameter 5-10 nanometer of composite nanometer particle.
2, the high-stability Fc/SiO that has core/shell structure
2The preparation method of composite nanometer particle, it is characterized in that with the molysite being raw material, molysite is frerrous chloride, ferric trichloride, ferric nitrate, ferric sulfate, basic ferric acetate or praseodynium iron, organic acid is a complexing agent, described organic acid is citric acid, nitroso triacetic acid, N-HEDTA or ethylenediamine tetra-acetic acid, molysite and organic acid mol ratio are 1: 1.0～1: 3.0, with absolute ethyl alcohol or isopropyl alcohol is that solvent forms even non-aqueous sol, the complex reaction temperature is 50-80 ℃, reaction time 4-10 hour; Add tetraethoxysilance, form xerogel through the pervaporation desolventizing, organic matter is removed in preroast in the air, at H
2In the atmosphere under the different temperatures reduction promptly obtain having the high-stability Fc/SiO of core/shell structure less than 10 nanometers
2Composite nanometer particle; Wherein evaporating the desolventizing temperature is 70-90 ℃; Xerogel pre-calcination temperature in air is 400-500 ℃, roasting time 4-10 hour; Reduction temperature is 500-900 ℃ in hydrogen, and the recovery time is 3-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041128.9A CN1290648C (en) | 2004-06-30 | 2004-06-30 | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041128.9A CN1290648C (en) | 2004-06-30 | 2004-06-30 | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594450A CN1594450A (en) | 2005-03-16 |
| CN1290648C true CN1290648C (en) | 2006-12-20 |
Family
ID=34664914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410041128.9A Expired - Fee Related CN1290648C (en) | 2004-06-30 | 2004-06-30 | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1290648C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100471601C (en) * | 2006-10-24 | 2009-03-25 | 中国科学技术大学 | A kind of synthesis method of silica hollow spheres containing noble metal nanoparticles |
| CN101599334B (en) * | 2009-04-21 | 2011-05-04 | 北京科技大学 | Preparation method of FeSiAl soft magnetic materials with high resistivity and high magnetic conductivity |
| CN102129902B (en) * | 2011-03-08 | 2012-06-27 | 吉林大学 | Method for preparing magnetic silica composite particles |
| CN102284706B (en) * | 2011-08-15 | 2013-04-24 | 华南理工大学 | Nanoscale zero-valent iron stable in air and preparation method for the same |
| CN102965074B (en) * | 2012-11-30 | 2015-08-26 | 钢铁研究总院 | A kind of nanoparticle for absorbing microwave and synthetic method thereof |
| CN103242802B (en) * | 2013-05-16 | 2014-12-17 | 南京航空航天大学 | Fabrication Method of Hollow Fe/Fe3O4@SiO2 Nanostructures with Tunable Absorbing Properties |
| CN103268801A (en) * | 2013-05-24 | 2013-08-28 | 南京航空航天大学 | FexOy/SiO2 composite material and preparation method thereof |
| US11285539B2 (en) * | 2016-05-13 | 2022-03-29 | University Of Maryland, College Park | Synthesis and functionalization of highly monodispersed iron and Core/Iron oxide shell magnetic particles with broadly tunable diameter |
| CN105965012B (en) * | 2016-06-07 | 2018-01-02 | 广州新莱福磁电有限公司 | A kind of method of soft-magnetic alloy powder body Surface coating silica insulation film layer |
| CN107321295B (en) * | 2017-08-02 | 2020-04-07 | 浙江理工大学 | Bell type structure Fe @ SiO2Composite microsphere, preparation method and application thereof |
| JP7179617B2 (en) * | 2017-10-04 | 2022-11-29 | 株式会社ダイヤメット | Silica-based insulation-coated soft magnetic powder and method for producing the same |
| CN109053127B (en) * | 2018-07-20 | 2021-03-02 | 济南大学 | A method for rapidly preparing high surface area porous FeOx/SiO2 composite material, obtained porous material and application |
| CN112509792B (en) * | 2020-11-25 | 2022-06-14 | 杭州电子科技大学 | A low power consumption, high DC bias magnetic core and its application |
| CN116130196A (en) * | 2022-11-29 | 2023-05-16 | 浙江工业大学 | High-frequency low-loss nanometer soft magnetic composite material and preparation method thereof |
| CN117728038B (en) * | 2023-08-08 | 2024-12-17 | 荣耀终端有限公司 | Preparation method and system of lithium battery |
-
2004
- 2004-06-30 CN CN200410041128.9A patent/CN1290648C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1594450A (en) | 2005-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1290648C (en) | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same | |
| Chen et al. | Preparation and magnetic properties of nickel nanoparticles via the thermal decompositionof nickel organometallic precursor in alkylamines | |
| Song et al. | Preparation and magnetic properties of SrFe12O19/Ni0. 5Zn0. 5Fe2O4 nanocomposite ferrite microfibers via sol–gel process | |
| Roca et al. | Structural and magnetic properties of uniform magnetite nanoparticles prepared by hightemperature decomposition of organic precursors | |
| Amara et al. | Solventless thermal decomposition of ferrocene as a new approach for one-step synthesis of magnetite nanocubes and nanospheres | |
| Liu et al. | Preparation and characterization of shuttle-like α-Fe2O3 nanoparticles by supermolecular template | |
| CN1812007A (en) | High-stability Fc/Al203 composite nano particles with nuclear/shell structure and producing method | |
| Cannas et al. | How to tailor maghemite particle size in γ-Fe 2 O 3–SiO 2 nanocomposites | |
| Wang et al. | Highly dispersed spinel (Mg, Ca, Ba)-ferrite nanoparticles: Tuning the particle size and magnetic properties through a modified polyacrylamide gel route | |
| Sivakumar et al. | Structural, thermal, dielectric and magnetic properties of NiFe2O4 nanoleaf | |
| Liu et al. | High-yield synthesis and characterization of monodisperse sub-microsized CoFe2O4 octahedra | |
| CN109604628B (en) | Preparation method of ordered phase iron platinum nano-particles and cobalt platinum nano-particles | |
| El-Sheikh et al. | Magnetic behavior of cobalt ferrite nanowires prepared by template-assisted technique | |
| Liu et al. | Morphology and magnetic properties of α-Fe2O3 particles prepared by octadecylamine-assisted hydrothermal method | |
| Wang | Facile hydrothermal synthesis of ZnCo2O4 nanostructures: controlled morphology and magnetic properties | |
| Karakassides et al. | Magnetic Fe 2 O 3–Al 2 O 3 composites prepared by a modified wet impregnation method | |
| Gandha et al. | Effect of ${\rm RuCl} _ {3} $ on Morphology and Magnetic Properties of CoNi Nanowires | |
| Suo et al. | Effect of Al 3+ ion-substituted Ni–Mg–Co ferrite prepared by sol–gel auto-combustion on lattice structure and magnetic properties | |
| Song et al. | Magnetic hard/soft nanocomposite ferrite aligned hollow microfibers and remanence enhancement | |
| JP2012197473A (en) | Method for synthesizing metal or alloy nanoparticle by supercritical hydrothermal reaction under reductive atmosphere | |
| El-Sheikh et al. | Morphological investigation and magnetic properties of nickel zinc ferrite 1D nanostructures synthesized via thermal decomposition method | |
| CN1817786A (en) | Two-dimensional fractional standing point array with ordered Fe/SiO2 composite nanometer particle and production thereof | |
| Sun et al. | Magnetite hollow spheres: solution synthesis, phase formation and magnetic property | |
| Valdés-Solís et al. | Facile synthetic route to nanosized ferrites by using mesoporous silica as a hardtemplate | |
| CN101567242A (en) | Method for preparing magnetic nano composite particles of FeCr alloy dispersed in ceramic crystal grain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |