CN100505116C - Fe/(SiO-[2]+C) core-shell composite nanometer particle with high stability and method for preparing same - Google Patents
Fe/(SiO-[2]+C) core-shell composite nanometer particle with high stability and method for preparing same Download PDFInfo
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- CN100505116C CN100505116C CNB2004100655090A CN200410065509A CN100505116C CN 100505116 C CN100505116 C CN 100505116C CN B2004100655090 A CNB2004100655090 A CN B2004100655090A CN 200410065509 A CN200410065509 A CN 200410065509A CN 100505116 C CN100505116 C CN 100505116C
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- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims description 22
- 239000011258 core-shell material Substances 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000002904 solvent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- VMPBCHQCVVBTLK-UHFFFAOYSA-N ethyl acetate silicic acid Chemical compound C(C)(=O)OCC.[Si](O)(O)(O)O VMPBCHQCVVBTLK-UHFFFAOYSA-N 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000008016 vaporization Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 description 14
- 230000005415 magnetization Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000012792 core layer Substances 0.000 description 1
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- 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
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Abstract
It is a compound nanometer particles of Fe/(SiO#-[2]+C) nucleus or shell with high stability. The process method comprises the following steps: to use iron salt as material and citric acid or other organic acid and organic amine as bonding agent and non-water ethanol as solve agent to form even non-water glue; to join silicic acid ethyl acetate and after vaporizing and condense to form solid glue; to pre-sinter in the air to remove the organic material; to deoxidize in H#-[2] and different temperatures to get the particles.
Description
One, technical field
The present invention relates to a kind of Fe/ (SiO with core/shell structure, high magnetic intensity, high stability
2+ C) composite nanometer particle and preparation method thereof.
Two, background technology
Metallic iron is a kind of metal of magnetic moment maximum in the magnetic transition elements.The metallic iron 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, soft magnetism, 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 requirements is high, be not suitable for large-scale production.We once adopted and prepare the surface at collosol and gel in conjunction with hydrogen reduction method and be coated with SiO
2Protective layer is less than 10 nano iron particles, though have high non-oxidizability, along with the fast development of industry, has a higher requirement for anti-oxidant.
Three, summary of the invention
The objective of the invention is to seek a kind of new preparation method, prepare have core/shell structure, the Fe/ (SiO of high magnetic intensity, high stability
2+ C) composite 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.Have saturation magnetization height, good soft magnet performance that coercive force 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, and simultaneously, by the flow and the time of control hydrocarbon gas gas, the thickness of charcoal shell also 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, citric acid is a complexing agent, and absolute ethyl alcohol is that solvent forms even colloidal sol (non-aqueous sol), adds tetraethoxysilance, forms gel through evaporation and concentration, and organic substance 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
2Composite nanometer particle feeds hydrocarbon gas again in insulation more than 400 ℃, is incubated more than three hours more than 750 ℃ in argon gas then, can obtain the Fe/ (SiO of high stability
2+ C) core/shell composite nanoparticle.The mol ratio of molysite and citric acid is 1:1.0～1:3.0; The complex reaction temperature is preferably above room temperature, especially is 50-80 ℃, 4-10 hours reaction time; Tetraethoxysilance is as SiO
2The silicon source of shell, SiO
2Covering amount be 1-30% (weight ratio); The evaporation and concentration temperature is 70-90 ℃; Xerogel calcined temperature in air is 400-500 ℃, roasting time 4-10 hours; Reduction temperature is 500-900 ℃ in hydrogen, and the recovery time is 3-10 hours, and the logical hydrocarbon gas time is 0.1-0.5 hour.With the iron particle of method preparation of the present invention, particle size distribution is comparatively even, is generally 40-200 nanometers, saturation magnetization 120-190Am
2/ kg.The also easily oxidation of long-time placement under the air at room temperature condition of simple iron parcel silicon oxide particle also is unfavorable for practical application.And the Fe/ (SiO with core/shell structure of the present invention's preparation
2+ C) composite nanometer particle at room temperature long-term stability be present in the air.
The former collosol and gel of the present invention prepares Fe/SiO
2On the basis of composite nanometer particle technology, down fed hydrocarbon gas 0.1-1 hour by simple 300-800 ℃, 750-1000 ℃ of insulations 2-7 hours in argon gas at last.Preparation technology is simple, and product stability height, product cut size are distributed as 50-200 nanometers, and the thickness of charcoal and silica is about 10-30 nanometers.Fed hydrocarbon gas 0.1 hour as 400 ℃, insulation can obtain the higher Fe/ (SiO of antioxygenic property in four hours in argon gas more than 750 ℃ again
2+ C) composite nanometer particle.
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.Described hydrocarbon gas is first-butane, ethene, acetylene etc.
Product with the present invention preparation carries out structure and performance characterization by following means: the thing that the D/Max-RA rotarting anode X-ray diffractometer (XRD) that adopts Japanese Rigaku company to produce is determined magnetic nanometer particles mutually; Utilize the shape and size of JEM-200CX transmission electron microscope (TEM) the Direct observation product that Japanese JEOL company produces; 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.By the flow and the time of control hydrocarbon gas gas, the thickness of charcoal shell also can be adjusted arbitrarily in very wide scope.Thereby antioxygenic property also can be guaranteed by the thickness that strengthens the charcoal shell.
Four, description of drawings
Fig. 1 is in embodiment 2 and 3 preparation process, and the XRD spectra of the product that obtains illustrates after argon gas atmosphere is handled the Fe in the product
3The content of C significantly reduces, and core layer is mainly single cube α-Fe phase.
Fig. 2 is embodiment 1,2, in 3 and 4 preparation process, and the Magnetic Measurement result of the product that obtains.Illustrate that along with the parcel of charcoal, saturation magnetization descends, handle the back owing to the Fe in the product through argon gas atmosphere
3The content of C significantly reduces α-Fe and increases, so saturation magnetization increases.
Fig. 3 is the product magnetic spectrum measurement result of embodiment 3 preparations, shows that the shell of surface parcel charcoal can effectively reduce eddy current loss, thereby can significantly improve the high frequency characteristics of product.
Fig. 4 is in embodiment 3 preparation process, and the HRTEM photo of the product that obtains illustrates surface coated C and SiO
2The thickness of shell is approximately 6nm, and α-Fe examines by C and SiO
2Shell well is wrapped in the inside.
Five, embodiment
Below be embodiments of the invention (agents useful for same is a chemical pure among the embodiment).
Embodiment 1: under the strong mixing, 0.01mol ferric trichloride and 0.015mol citric acid are dissolved in the 100mL absolute ethyl alcohol, 60 ℃ continue to stir 6 hours, form homogeneous transparent colloidal sol; Add the 0.1mL 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.Fed hydrocarbon gas 0.1 hour down at 600 ℃ then.The product that obtains is to have amorphous Si O
2With the charcoal shell, core is the α-Fe of cube crystalline phase and the Fe of more amount
3The composite nanometer particle of C.Magnetic Measurement the results are shown in Figure 2, saturation magnetization 193.61Am
2/ kg.
Use FeCl
24H
2O, ferric nitrate obtain result similar to the above.
Above-mentioned molysite can with 0.02mol HEDTA or, EDTA also obtains equifinality.
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 0.1mL tetraethoxysilance, 80 ℃ of evaporation and concentration are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air places 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then, feeds methane, ethane or butane, ethene, acetylene etc. 0.5 hour down at 400 ℃ then.Hydrocarbon gas does not have remarkable difference.The product that obtains is to have amorphous Si O
2With the charcoal shell, core is the α-Fe of cube crystalline phase and the Fe of more amount
3The composite nanometer particle of C.
Magnetic Measurement the results are shown in Figure 2, saturation magnetization 76.53Am
2/ kg.
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, form homogeneous transparent colloidal sol; Add the 0.1mL tetraethoxysilance, 80 ℃ of evaporation and concentration are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air, place 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then, feed methane, ethane or butane, ethene, acetylene etc. 0.5 hour down at 400 ℃ then, in argon gas atmosphere, be incubated four hours under 750 ℃ at last.The product that obtains is to have amorphous Si O
2With the charcoal shell, core is the composite nanometer particle of α-Fe of cube crystalline phase and the Fe of minute quantity
3C.Magnetic Measurement the results are shown in Figure 2, saturation magnetization 116Am
2/ kg.Comparison example is 2 Magnetic Measurement results show, after in argon gas, annealing, and more Fe
3C changes α-Fe into, so saturation magnetization increases.The Magnetic Measurement result of comparison example 1 shows that owing to mixing of nonmagnetic charcoal, saturation magnetization reduces.
Embodiment 4: 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 0.1ml tetraethoxysilance, 80 ℃ of evaporation and concentration are until generating xerogel; Xerogel 450 ℃ of preroast 3 hours in air places 800 ℃ of reduction of tube furnace hydrogen atmosphere 4 hours then, feeds hydrocarbon gas 0.1 hour down at 450 ℃ then, 800 ℃ of insulations 4 hours down in argon gas atmosphere at last.The hydrocarbon gas feeding time is 0.1 hour, and the content of charcoal reduces in the products therefrom.The magnetic property influence of the product that logical first-butane, ethene, acetylene time are right is very big.Magnetic measurement results is seen Fig. 2; Feeding first-butane, ethene, acetylene time are that the magnetization of 0.1 hour gained sample is 176.35Am
2/ kg shows, the logical hydrocarbon gas time is short more, and the shell of the charcoal of parcel is thin more, so saturation magnetization is big more.The hydrocarbon gas feeding time is 0.1 hour, and 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.Electronic Speculum and high resolution electron microscopy observed result are seen Fig. 4, and Magnetic Measurement the results are shown in Figure 2, and the magnetic spectrum measurement result is seen Fig. 3.High resolution electron microscopy observation shows that the product that obtains is has amorphous Si O
2With the charcoal shell, core is the composite nanometer particle of the α-Fe of cube crystalline phase.
By above-mentioned condition, fed hydrocarbon gas 0.8 hour down at 350 and 800 ℃, in argon gas atmosphere, be incubated 6 hours under 1000 ℃ at last.First-butane, ethene or acetylene feed time lengthening, and the charcoal parcel is more in the products therefrom.The magnetization obviously reduces, and is about 50-60Am
2/ kg.Temperature retention time length makes the performance of product more stable.
Claims (6)
1, the Fe/ (SiO of high stability
2+ C) core/shell composite nanoparticle is characterized in that with the nano iron particles being core, surperficial coated Si O
2The composite nanometer particle that+C shell is formed with core/shell structure.
2, the Fe/ (SiO of high stability
2+ C) the preparation method of core/shell composite nanoparticle is a raw material with the molysite, and citric acid or other organic acid, organic amine are complexing agent, absolute ethyl alcohol is that solvent forms even non-aqueous sol, adds tetraethoxysilance, forms gel through evaporation and concentration, organic substance is removed in preroast in the air, at H
2Temperature is 500-900 ℃ of reduction in the atmosphere, obtains having the high-stability Fc/(SiO of core/shell structure
2+ C) composite nanometer particle; It is characterized in that down feeding hydrocarbon gas 0.1-1 hour at 300-800 ℃ again after the reduction, 750-1000 ℃ of insulations 2-7 hours in argon gas at last obtain the Fe/ (SiO of high stability
2+ C) core/shell composite nanoparticle.
3, by the Fe/ (SiO of the described high stability of claim 2
2+ C) the preparation method of core/shell composite nanoparticle is characterized in that the temperature of above-mentioned evaporation and concentration is 70-100 ℃; Xerogel pre-calcination temperature in air is 300-600 ℃, 3-10 hours preroast time; Recovery time is 3-10 hours in hydrogen;
4, by the Fe/ (SiO of the described high stability of claim 2
2+ C) the preparation method of core/shell composite nanoparticle, the mol ratio that it is characterized in that molysite and citric acid is 1:1.0～1:3.0; The complex reaction temperature is 50-90 ℃, 4-10 hours reaction time.
5, by the Fe/ (SiO of the described high stability of claim 2
2+ C) the preparation method of core/shell composite nanoparticle, it is characterized in that the process that forms even non-aqueous sol is, described molysite is that the frerrous chloride, ferric trichloride, ferric nitrate, ferric sulfate or the basic ferric acetate that are dissolved in alcohol are dissolved in and form non-aqueous solution in the absolute ethyl alcohol, form homogeneous transparent colloidal sol with citric acid complex, the mol ratio of molysite and citric acid is 1:1.0～1:3.0; The complex reaction temperature is 50-90 ℃, 4-10 hours reaction time.
6, by the described high-stability Fc of claim 2/(SiO
2+ C) the preparation method of core/shell composite nanoparticle is characterized in that tetraethoxysilance is as SiO
2The silicon source of shell, SiO
2Covering amount be 1-30% weight ratio; The evaporation and concentration temperature is 70-90 ℃, until generating xerogel.
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| CN103192073B (en) * | 2013-03-29 | 2015-12-23 | 湖南科技大学 | A kind of nanometer iron silicon compound particle of three-layer nuclear shell structure and preparation method and application |
| CN105869516B (en) * | 2016-06-12 | 2018-11-09 | 王连杰 | A kind of macroscopic nanometer antifalsification label |
| CN108117841A (en) * | 2016-11-29 | 2018-06-05 | 中芯国际集成电路制造(上海)有限公司 | A kind of lapping liquid, the method and chemical and mechanical grinding method for preparing lapping liquid |
| CN111168078A (en) * | 2020-03-06 | 2020-05-19 | 无锡市东杨新材料股份有限公司 | Preparation method of iron-coated silicon core-shell composite powder |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4729785A (en) * | 1985-05-10 | 1988-03-08 | Basf Aktiengesellschaft | Preparation of acicular ferromagnetic metal particles consisting essentially of iron |
| CN1445797A (en) * | 2003-04-01 | 2003-10-01 | 吉林大学 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
| CN1539793A (en) * | 2003-04-21 | 2004-10-27 | 中国科学院理化技术研究所 | Method for preparing composite magneticparticle in submicro size by using Nano granules of magnet ironoxide to clad organic microsphere |
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2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4729785A (en) * | 1985-05-10 | 1988-03-08 | Basf Aktiengesellschaft | Preparation of acicular ferromagnetic metal particles consisting essentially of iron |
| CN1445797A (en) * | 2003-04-01 | 2003-10-01 | 吉林大学 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
| CN1539793A (en) * | 2003-04-21 | 2004-10-27 | 中国科学院理化技术研究所 | Method for preparing composite magneticparticle in submicro size by using Nano granules of magnet ironoxide to clad organic microsphere |
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