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
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- 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
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 10
- 229910052681 coesite Inorganic materials 0.000 title abstract 5
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 5
- 239000000377 silicon dioxide Substances 0.000 title abstract 5
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 5
- 229910052682 stishovite Inorganic materials 0.000 title abstract 5
- 229910052905 tridymite Inorganic materials 0.000 title abstract 5
- 239000002105 nanoparticle Substances 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 38
- 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 15
- 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
- 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
- 238000002360 preparation method Methods 0.000 claims description 20
- 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
- 239000005416 organic matter Substances 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
- 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
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000005298 paramagnetic effect Effects 0.000 abstract description 2
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 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
- 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
- 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
- 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
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- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a high stability Fe/SiO2 composite nanometer particle with core/shell structure, which is composed of a nanometer iron particle used as a core, and a shell whose surface is coated with SiO2. A method for preparing the composite nanometer particle comprises: iron salt is used as raw material, organic acid is used as a complexing agent, and anhydrous alcohol or isopropyl alcohol is used as solvent to form uniform non-aqueous sol; orthosilicate ethyl ester is added to form gel by dehydration through evaporation, preparatory roasting is carried out in air to remove organic substances, and reduction reaction is generated in H2 atmosphere at different temperatures to obtain high stability Fe/SiO2 composite nanometer particles with core/shell structure and diameters smaller than 10 nm. Non-aqueous solvent is adopted in the method, and no filtration washing step exists, so that the thickness of the SiO2 shell can be arbitrarily adjusted within a wide range. The preparing technology has the advantages of simplicity and easy process control and is suitable for large-scale production. The particle diameter of the product is smaller than 10 nm, the iron core is smaller than the super paramagnetic critical dimension, and the product has favorable soft magnetic properties of high saturation magnetization intensity and low coercivity.
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.
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