CN101332508A - Needle shaped porous iron granule cladded by silicon and manufacture method thereof - Google Patents
Needle shaped porous iron granule cladded by silicon and manufacture method thereof Download PDFInfo
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- CN101332508A CN101332508A CNA2007100428175A CN200710042817A CN101332508A CN 101332508 A CN101332508 A CN 101332508A CN A2007100428175 A CNA2007100428175 A CN A2007100428175A CN 200710042817 A CN200710042817 A CN 200710042817A CN 101332508 A CN101332508 A CN 101332508A
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Abstract
The invention provides an acicular porous iron particle coated by silicon and a preparation method thereof. The acicular porous iron particle comprises the following components with the weight proportions: 75-90% of Alpha-Fe and 10-25% of SiO2; the specific surface area is more than 65<2>/g, the oxidizing temperature is not less than 200 DEG C, and the specific saturation magnetization is not less than 130emu/g. The ultrafine porous iron particle coated with silicon dioxide which is made by the method of the invention can be stably stored in the air, has both high magnetic property and adsorbability, and is applicable for the application fields such as being directly used as magnetic target drug carrier and electromagnetic wave absorbing material and the like.
Description
Technical field
The present invention relates to a kind of porous iron granule and preparation method thereof, particularly adopt high temperature reduction and organosilicon reagent thermal decomposition to carry out the surface treatment method of ultra-fine porous iron granule.
Background technology
Developing safely and efficiently, drug delivery approach and technology are to promote the clinical drug key in application.No matter be to transmit or utilize body-internal-circulation to act on each position of whole body by local orientation, the medicine of clinical practice all needs to reach does not both have obvious toxic and side effects, can in the minimum dose scope, bring into play drug effect again, safe, cheap effective conveying of easily being accepted simultaneously by the patient.The solution of targeted drug success the problems referred to above.It conducts drugs to lesions position by targeting vector, and discharge medicine for a long time at lesions position, keep local higher drug concentration, and normal structure Chinese traditional medicine concentration is very low, the benefit of bringing is conspicuous: the use amount that 1) greatly reduces medicine; 2) improve curative effect of medication, reduced toxic and side effect.
At present, the magnetic target medicine under the external magnetic field guiding function be mostly magnetisable material as the target material, after surface modification,, thereby realize the target location at its surface grafting medicine; Or by compound target medicine carrier (Chinese invention patent for example, the application number: 031508189) utilize sorptive material absorption or discharge medicine, utilize magnetic material to carry out the target location of preparing of sorptive material and magnetic material.
But because targeting vector is a composite, wherein the ratio of magnetic material is lower, is unfavorable for the target location of carrier, has reduced the curative effect of targeted therapy.
Up to now, few about the open report of porous iron.Liyuan New Material Co Ltd, Changsha's (Chinese invention patent application publication number: CN1651614) adopt the alloy plating method, one step iron plating and nickel, make iron and nickel be deposited on non-metallic substrate surface after the conductionization processing with alloy form, the total amount and the ratio of two metal ion species in the control electroplating solution, the material that obtains thus is by the metallic framework of nickel and iron constituent material, nickel content is between 30%～50%, and all the other are iron, has prepared the porous iron nickel alloy material.
SEI Corporation's (Chinese invention patent application publication number: CN1168930) plating is carried out on the surface of conductive porous matrix material, remove matrix material, reduce coating then, obtain the porous iron material by roasting with iron.
China Geological Univ. Wuhan's (Chinese invention patent application publication number: CN1410198) adopt powder sintering, preliminary treatment by material, mixed slurry sintering in 350-800 ℃ temperature range that iron powder or iron filings, pore creating material and Foamex are made into then, sintering time is 0.5-2 hour, the tempering 2 hours under 200 ℃ of temperature of cooling back.When being raw material, can make porosity respectively greater than 65% and 75% porous iron with iron powder and iron filings.
The technology of above-mentioned patent and bibliographical information, having a significant defective is to be bulk material, therefore can not satisfy the needs that clinical practice and antiradar coatings are used.
Summary of the invention
The objective of the invention is to disclose a kind of ultra-fine porous iron granule and manufacture method thereof of coated with silica, overcome the not high shortcoming of magnetic target medicine carrier magnetic in the past, satisfy application demands such as magnetic target medicine carrier and suction ripple.
The ultra-fine porous iron granule of coated with silica of the present invention is the brown powder of a kind of particle diameter at 100～900nm, and its component and mass content comprise:
α-Fe 75～90%, SiO
210～25%, specific area is greater than 65m
2/ g, oxidizing temperature is not less than 200 ℃, and specific saturation magnetization is not less than 130emu/g;
Preferably, specific area is 65～150m
2/ g, 200～240 ℃ of oxidizing temperatures, specific saturation magnetization is 130～140emu/g;
The manufacture method of the ultra-fine porous iron granule of above-mentioned coated with silica comprises the steps:
(1) with α-Fe
2O
3H
2O (being called for short the α iron oxide yellow) dewaters under 300～550 ℃ of temperature, and dewatering time is cooled to obtain the α-Fe of porous below 40 ℃ at 15～45min then
2O
3(being called for short the α iron oxide red);
Said α iron oxide yellow can be to adopt the coprecipitation preparation, for example disclosed method is prepared in 1996 the 22nd volumes of East China University of Science's journal the 1st phase " acid system synthesizes the ultra-fine alpha-feooh process study of the aciculiform " document, perhaps adopt the commercially available prod, as the products such as the yellow L1916 of trade mark Sicotrans of BASF AG's production.Be preferably in the preparation process and the material that adopts surfactant to handle after the preparation, this processing method has had detailed report in Chinese invention patent publication number CN1884393 document, and the present invention repeats no more;
(2) the α iron oxide red of porous is handled with organic silicon solution:
The α iron oxide red of step (1) is dropped in the organic silicon solution, stirred 0.5～4 hour, drying removes solvent, and hydrogen is fed in the product, at 350～650 ℃ of following reduction reaction 1～12hr, reduces to room temperature, can obtain the ultra-fine porous iron granule of coated with silica;
The pressure of reduction reaction can be normal pressure or pressurization, is preferably normal pressure;
Said organic silicon solution is by organosilicon and solvent composition;
Said organosilicon is selected from ethyl orthosilicate or silicone oil etc. can decompose generation silica and not volatile organosilicon reagent at a certain temperature;
Said silicone oil is selected from more than one in methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methyl chloride phenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl ethylene silicone oil, methyl hydroxy silicon oil, ethyl containing hydrogen silicone oil or the hydroxyl hydrogen silicone oil, and wherein ethyl orthosilicate and kinematic viscosity are that the silicone oil of 0.6cs～100cs is preferred;
Said solvent is selected from the organic solvent of the effumability that methyl alcohol, ethanol or acetone etc. can dissolve each other with organosilicon reagent, and wherein ethanol or acetone are preferred;
The mass concentration of said organic silicon solution concentration is 1～20%, preferably 1.5～10%;
The use amount of organic silicon solution is amounted to SiO according to organosilicon
2Quality is 5～25% of the quality of α iron oxide red, and optimum is 7～21%;
Too low silica ratios causes α-Fe oxidized or spontaneous combustion easily in the product, and too high silica ratios then can reduce the ratio of α-Fe in the product and the specific saturation magnetization of product is descended.
The dip time of porous α iron oxide red in organic silicon solution can be between 0.5～4 hour, and shorter dip time influences the absorption uniformity of organosilicon on α iron oxide red surface, the heat endurance variation of end product; And longer dip time does not have influence to the heat endurance of end product, but uneconomical also unnecessary preferred dip time is 1～2 hour.
The dipping of porous α iron oxide red in organic silicon solution can carry out under common stirring condition.After dipping is finished, can adopt drying means commonly used to remove remaining above-mentioned solvent and obtain the α iron oxide red powder that organosilicon is handled.
The ultra-fine porous iron granule of the coated with silica of the present invention's preparation, stable in the air the depositing of energy both possessed high magnetic property, had absorption property again, was fit to directly as applications such as magnetic target medicine carrier and electromagnetic wave absorbent materials.
Description of drawings
The transmission electron microscope photo of Fig. 1 embodiment 2 products.
The X-ray diffraction spectrogram of Fig. 2 embodiment 2.
The specific embodiment
Do the change of some change for those skilled in the art as coatings such as silicone oil, the change of solvent, the change in reaction temperature and reaction time, the change of the oxide particle granularity of the used iron of source of iron all belongs within the scope of the present invention.Embodiments of the invention do not limit scope of invention.
Embodiment 1
Adopt 1996 the 22nd volumes of East China University of Science's journal the 1st phase " acid system synthesizes the ultra-fine alpha-feooh process study of aciculiform " document disclosed method to prepare 30g transparent iron bloom end, particle length is 120nm, be tiled on the square sheet metal of 50 centimetres of the length of sides, put into furnace temperature and be 350 ℃ heating furnace, take out behind the 15min, cooling;
Get 310ml ethyl orthosilicate mass concentration and be 8.0% ethanolic solution and place the 1000ml container, iron oxide red after the above-mentioned cooling is added in the teos solution, stir 2hr.Vacuum drying places powder in the tubular react furnace after removing residual solvent, and the outlet of reacting furnace is a normal pressure, feeds high-purity hydrogen; be warming up to 500 ℃; reduction reaction 6hr drops to room temperature in the protection of hydrogen, obtains the ultra-fine needle shaped porous iron granule of coated with silica.α-Fe 77.3% in the product, SiO
2Content is 22.5%, and the particle average length of product is 105nm, ASAP2400BET tester test specific area 140.8m
2It is 135emu/g that/g, TMP-7BH instrument test its specific saturation magnetization.
According to embodiment 1, different is that preliminary examination iron oxide yellow raw material replaces transparent iron bloom end with common pigments iron oxide yellow powder (Shanghai Yipin International Pigments Co., Ltd.'s 313 iron oxide yellows), dehydration temperaturre is 450 ℃, the mass concentration of ethyl orthosilicate ethanolic solution is 1.6%, the consumption of ethyl orthosilicate ethanolic solution is 571ml, reduction temperature is 600 ℃, obtains the ultra-fine needle shaped porous iron granule that silicon coats.Product is porous needle-like (seeing accompanying drawing 1) according to electron-microscopic analysis, and the scale 100nm of Fig. 1, particle average length 680nm, TMP-7BH instrument test it than saturation magnetization intensity 137emu/g, and ASAP2400BET tester test specific area is 68.5m
2/ g; X-ray diffraction test (seeing accompanying drawing 2) shows that iron exists mutually with α-Fe in the product, the relevant peaks that the oxide of iron do not occur, α-Fe content 88.9% wherein, the obvious characteristics peak does not appear in silica in X-ray spectrum, show that clad silica exists with unformed, its content is 10.3%.
Embodiment 3
According to embodiment 2, different from dimethicone (model 201-20, meet HG/T 2366-92 " dimethicone ", Grade A) replaces ethyl orthosilicate, dewatering time is 30min, the mass concentration of 201-20 silicone oil ethanolic solution is 5%, and reduction temperature is 600 ℃, obtains the ultra-fine needle shaped porous iron granule that silicon coats.The average length of product is 675nm, and the TMP-7BH instrument is tested it than saturation magnetization intensity 136emu/g, and ASAP2400BET tester test specific area is 68.1m
2/ g, α in the product-Fe content 87.5%, dioxide-containing silica are 11.3%.
Claims (10)
1. the needle shaped porous iron granule that coats of silicon is characterized in that its component and mass content comprise:
α-Fe 75～90%, SiO
210～25%, specific area is greater than 65m
2/ g, oxidizing temperature is not less than 200 ℃, and specific saturation magnetization is not less than 130emu/g.
2. the needle shaped porous iron granule that silicon according to claim 1 coats is characterized in that specific area is 65～1 50m
2/ g, 200～240 ℃ of oxidizing temperatures, specific saturation magnetization is 130～140emu/g.
3. make the method for the ultra-fine porous iron granule of claim 1 or 2 described coated with silica, it is characterized in that, comprise the steps:
(1) with α-Fe
2O
3H
2O dewaters, and obtains the α-Fe of porous
2O
3
(2) with the α-Fe of the porous of step (1)
2O
3Drop in the organic silicon solution, stirred 0.5～4 hour, drying removes solvent, and hydrogen is fed in the product, at 350～650 ℃ of following reduction reaction 1～12hr, reduces to room temperature, can obtain the ultra-fine porous iron granule of coated with silica;
Said organic silicon solution is by organosilicon and solvent composition.
4. method according to claim 3 is characterized in that said organosilicon is selected from ethyl orthosilicate or silicone oil.
5. method according to claim 3, it is characterized in that said silicone oil is selected from more than one in methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methyl chloride phenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl ethylene silicone oil, methyl hydroxy silicon oil, ethyl containing hydrogen silicone oil or the hydroxyl hydrogen silicone oil.
6. method according to claim 3 is characterized in that said solvent is selected from methyl alcohol, ethanol or acetone.
7. method according to claim 3 is characterized in that, the mass concentration of said organic silicon solution concentration is 1～20%.
8. method according to claim 3 is characterized in that the use amount of organic silicon solution is amounted to SiO according to organosilicon
2Quality is 5～25% of the quality of α iron oxide red.
9. method according to claim 3 is characterized in that α-Fe
2O
3H
2O dewaters under 300～550 ℃ of temperature, and dewatering time is cooled to below 40 ℃ then at 15～45min.
10. method according to claim 3 is characterized in that, said α iron oxide yellow is to adopt the coprecipitation preparation, adopts surfactant to handle in preparation process and after the preparation.
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| CNA2007100428175A CN101332508A (en) | 2007-06-27 | 2007-06-27 | Needle shaped porous iron granule cladded by silicon and manufacture method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103650217A (en) * | 2011-05-30 | 2014-03-19 | 国立大学法人群马大学 | Negative-electrode active material for lithium ion secondary cell, and negative electrode and secondary cell using negative-electrode active material for lithium ion secondary cell |
| CN105780087A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院大连化学物理研究所 | Preparation method for electro-oxidation synthesis of one-dimensional nano-oxide structure |
| CN109265127A (en) * | 2018-11-19 | 2019-01-25 | 河北工业大学 | A kind of preparation method of 3D printing high-strength and high-ductility microwave defense material |
-
2007
- 2007-06-27 CN CNA2007100428175A patent/CN101332508A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103650217A (en) * | 2011-05-30 | 2014-03-19 | 国立大学法人群马大学 | Negative-electrode active material for lithium ion secondary cell, and negative electrode and secondary cell using negative-electrode active material for lithium ion secondary cell |
| CN103650217B (en) * | 2011-05-30 | 2017-02-15 | 国立大学法人群马大学 | Lithium ion secondary cell |
| CN105780087A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院大连化学物理研究所 | Preparation method for electro-oxidation synthesis of one-dimensional nano-oxide structure |
| CN105780087B (en) * | 2014-12-16 | 2018-03-20 | 中国科学院大连化学物理研究所 | The preparation method of Electric oxidative synthesis 1-dimention nano oxide structure |
| CN109265127A (en) * | 2018-11-19 | 2019-01-25 | 河北工业大学 | A kind of preparation method of 3D printing high-strength and high-ductility microwave defense material |
| CN109265127B (en) * | 2018-11-19 | 2021-09-07 | 河北工业大学 | Preparation method of high-strength high-toughness electromagnetic protection material for 3D printing |
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Open date: 20081231 |