CN1554727A - Method for preparing carbon coated nano metal material using biological material-starch as substrate - Google Patents
Method for preparing carbon coated nano metal material using biological material-starch as substrate Download PDFInfo
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- CN1554727A CN1554727A CNA2003101192000A CN200310119200A CN1554727A CN 1554727 A CN1554727 A CN 1554727A CN A2003101192000 A CNA2003101192000 A CN A2003101192000A CN 200310119200 A CN200310119200 A CN 200310119200A CN 1554727 A CN1554727 A CN 1554727A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 229920002472 Starch Polymers 0.000 title claims abstract description 30
- 239000008107 starch Substances 0.000 title claims abstract description 30
- 239000007769 metal material Substances 0.000 title claims description 9
- 239000000758 substrate Substances 0.000 title 1
- 239000002086 nanomaterial Substances 0.000 claims abstract description 38
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 235000011837 pasties Nutrition 0.000 claims description 5
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- -1 metal oxide compound Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 239000011553 magnetic fluid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- 229960004887 ferric hydroxide Drugs 0.000 abstract 1
- 238000003384 imaging method Methods 0.000 abstract 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract 1
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- 238000011160 research Methods 0.000 description 9
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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Abstract
The present invention belongs to the field of the crossed nano carbon material and biological material technology, and relates to the temperature control carbonizing process for preparing carbon coated nano material under hydrogen atmosphere with starch as precursor material. Starch as carbon source precursor and ferric hydroxide prepared with ferrite nitrate are mixed homogeneously and the mixture is dried and ground to obtain material pre-mixture. The material pre-mixture is carbonized under reduction amtosphere and controlled temperature to prepare carbon coated nano material material. The present invention has low cost, simple process, controllable condition and other advantags, and the product may be large scale produced and widely used in high density magnetic record material, magnetic fluid nuclear magnetic resonant imaging and other fields.
Description
Technical field
The invention belongs to the interleaving techniques field of carbon nano material and biomaterial, relating to a kind of is that matrix adopts the reduction charring process to prepare the method for carbon-coated nano material (Carbon encapsulatednanomaterials) with starch.
Background technology
For being that matrix adopts the reduction charing to prepare the method for carbon-clad metal nano material with biomaterial-starch, yet there are no corresponding report at home and abroad,
Along with the fast development of science and technology, " nanotechnology " causes worldwide vibrations as a kind of new ideas, will bring brand-new variation to technical field.Because nano material has special structure and peculiar physico-chemical property, has caused various countries scientific research personnel's extensive concern, becomes new research focus.The research of carbon nano science starts from the discovery of soccerballene in 1985, after this obtains constantly development, and carbon nanotube, nano-sized carbon green onion and metal filled carbon nano-structured novel material are found in succession.These nano-carbon materials have particular structure and character, and brand-new scientific research field has been opened up in their discovery, has broad application prospects in Condensed Matter Physics, Materials science and fields such as chemistry and electronic technology.
As a kind of novel carbon composite nano-material, its preparation and property research have become the research focus of material science to carbon-coated nano metallic substance (Carbon encapsulated metal nanomaterials or Metalfilled carbon nanomaterials).The carbon-clad metal nano material is to find that in resulting cigarette ash it is the LaC that is coated by multilayer graphite when adopting the arc process evaporation to gasify the graphite anode rod of mixing La in 1993 by people such as U.S. Rouff group and Japanese Tomita
2Nano material.Carbon coats the synthetic extensive concern of scientist to the carbon-clad metal nano material that caused of success of La nano material.In the past during the decade, people increase day by day to the research interest of the carbon-clad metal nano material of this soccerballene cage modle structure, its major cause is summed up as following 2 points: one, the carbon-clad metal nano material has huge potential application at numerous areas, and these fields comprise: magnetic recording material, cancer diagnosis and treatment, xeroprinting, magnetic fluid and Magnetic resonance imaging etc.; They are two years old, the nanometer materials that coated by graphite have unique physics and chemical property, the outsourcing carbon of carbon-coated nano material forms enclosed space makes the nano material and the environment that are coated isolated, make it can stable existence, this have just further expanded the practical application space of those unsettled nano materials in air.
Up to the present, the method for preparing the carbon-coated nano material of bibliographical information mainly contains following several: arc process, particle beam (laser, electronics, ion) sputtering method, high-temperature heat treatment method and chemical Vapor deposition process etc.; These technological methods respectively have characteristics but also have the defective that himself can't overcome.Wherein arc process is as the processing method that is used to prepare the carbon-clad metal nano material the earliest, remain main method of preparation carbon-clad metal nano material at present: generally be earlier the centre of Graphite Electrodes (anode) to be emptied, and insert the metallic substance that intend to coat or the persursor material of its oxide compound and rare earth element, adopt of the combined electrode evaporation gasification of the mode of arc-over again with graphite and metallic substance, bar-shaped sedimental centre on graphite cathode and be deposited in the cigarette ash of wall and contain the carbon-clad metal nano particle, but also other a large amount of nano-carbon material of association simultaneously; The productive rate of the target product of arc process is lower, product structure is restive, and technological method itself is difficult to further amplification.Source (device) takes place in the particle that the particle sputtering method needs to produce high energy particle usually, and to having relatively high expectations of plant and instrument, the possibility of actual production is little; People increase to some extent to the research interest of chemical Vapor deposition process at present, it is a kind of fairly simple method, the process ratio is easier to control, but this method adopts raw material to be generally organometallics, and the productive rate of these compounds comparison costliness itself and target product neither be too desirable.Except that above-mentioned several common methods, also have some other preparation method: as high temperature pyrolytic cracking (HTP), explosion method etc., but these method researchs are less, and operation is difficulty relatively, also has far distance from practical application.
Summary of the invention
In order to solve problems such as complex process, by product that present preparation carbon-coated nano material exists are many, the object of the present invention is to provide a kind of is matrix with biomaterial-starch cheap and easy to get, adopt reduction temperature control charring process to prepare the method for carbon-clad metal nano material, prepare the compound of starch and metal oxide by sequence of operations, under reducing atmosphere (hydrogen), this compound is carried out temperature control charing pyrolysis then and obtain a large amount of carbon-clad metal nano materials.Cost is low, productive rate is high, simple to operate.
Technical scheme of the present invention is:
Be that matrix prepares the carbon-clad metal nano material and comprises two main processes with starch, the one, the preparation of charing presoma-starch and metal oxide compound; The 2nd, the compound of the starch that obtains and metal oxide is carried out charing handle under the condition of Controllable Temperature.Concrete processing step is:
(1) takes by weighing Zulkovsky starch 20.00g, add in the small beaker that contains the 5ml deionized water (50ml), stir into pasty state with glass stick; Take by weighing 1.00g Fe (NO
3)
39H
2O also is dissolved in it in 50ml deionized water, and slowly adding a mole dosage ratio in this solution is the NaOH of 3: 1 0.1mol/L, obtains Fe (OH)
3Throw out is again with Fe (OH)
3Throw out joins in the above-mentioned starch paste, obtains the brown paste after fully stirring, and puts into baking oven in 100 ℃ of dry 2h down, and it is standby with mortar dried sample to be ground into fine powder;
(2) the compound powder of the starch metal oxide of 1.00～2.00g is put into quartz boat, then quartz boat is placed the central authorities of the crystal reaction tube in the tubular type charring furnace, with hydrogen with 20cm
3The speed of/min feeds reaction tubes, and flow is 20～50cm
3/ min, the speed with 5～10 ℃/min under hydrogen atmosphere is warmed up to 800～950 ℃ with charring furnace, and is incubated 1～4h;
(3) after carbonization reaction finishes, hydrogen is switched to nitrogen, speed is 50cm
3/ min makes reaction system be cooled to room temperature under nitrogen protection, and a large amount of black carbides that generate in quartz boat are the carbon-clad metal nano material.
Metal oxide can be by iron nitrate or iron(ic) chloride, Xiao Suangu and single nickel salt preparation.The diameter of crystal reaction tube is 30mm, and length is 600mm.
The invention has the beneficial effects as follows:
(1) the present invention is that a kind of employing low-temperature carbonization technology prepares carbon-coated nano material method, and process is simple, easy to operate, process is amplified easily, and very big practical value is being arranged aspect the preparation of carbon-coated nano material.
(2) the present invention is to be carbon matrix precursor with a kind of biomaterial-starch, and raw material sources conveniently are easy to get, and compares with raw material of other preparation carbon-clad metal nano material, and is with low cost.
(3) the present invention obtains charing presoma compound by simple forerunner's reason process, prepares the carbon-coated nano material through low-temperature carbonization again, and actually operating is simple.
(4) the present invention adopts the simple heating device can finish the charing treating processes, and this technology is not high to equipment requirements, and parameter is controlled easily, is easy to realize industrialization.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
(A B) is the low power and the high power transmission electron microscope photo of the carbon-encapsulated iron nano material that makes by the embodiment of the invention 1 processing condition to Fig. 1.
Fig. 2 is the XRD spectra of the carbon-encapsulated iron nano material that makes by the embodiment of the invention 1 processing condition.
Fig. 3 is the high power transmission electron microscope photo of the carbon-encapsulated iron nano material that makes by the embodiment of the invention 2 processing condition.
Fig. 4 is the high power transmission electron microscope photo of the carbon-encapsulated iron nano material that makes of the processing condition by embodiments of the invention 3.
From Fig. 1 (A, B) on the photo as can be seen, the carbon-coated nano particle shape is torispherical and has ideal shell nuclear clad structure, coats carbon layer about 5～8nm, particle diameter is between 20～100nm, and is better dispersed.
As can be seen from Figure 2, the carbon-encapsulated iron nano particle is monometallic phase (sees among the figure and mark), and carbon-coating has tangible graphite-structure.
As can be seen, the carbon-coated nano particle shape is torispherical and has ideal shell nuclear clad structure from Fig. 3 photo, and the thickness that coats carbon-coating is about 2～5nm.
As can be seen, the carbon-coated nano particle shape is torispherical and has ideal shell nuclear clad structure from Fig. 4 photo, and the thickness that coats carbon-coating is about 5～7nm.
Embodiment
Embodiment 1
Take by weighing Zulkovsky starch 2.00g, join (50ml) in the small beaker that contains the 5ml deionized water, stir into pasty state with glass stick.Take by weighing 0.10g Fe (NO again
3)
39H
2O also is dissolved in it in 50ml deionized water, and adding a mole dosage ratio lentamente then in this solution is the NaOH of 3: 1 0.1mol/L, obtains Fe (OH)
3Precipitation is with Fe (OH)
3Precipitation joins in the aforementioned starch paste that obtains, and obtains the brown paste after fully stirring, and puts into baking oven dry 2h under 100 ℃, with mortar the exsiccant sample is ground into fine powder.
The above-mentioned fine powder of 1.00g is put into quartz boat, place the central authorities of the crystal reaction tube (diameter 30mm, length 600mm) of tubular type charring furnace then; Thereupon with hydrogen with 20cm
3The speed of/min feeds reaction tubes, and the speed with 5 ℃/min is warmed up to 900 ℃ and constant temperature 4h with charring furnace then.Carbonization reaction switches to nitrogen (50cm with hydrogen after finishing
3/ min), make system under nitrogen protection, be cooled to room temperature.After carbonization reaction finishes, take out in the quartz boat, wherein a large amount of black carbides of Sheng Chenging are that the carbon-clad metal nano material is just in quartz boat.
Embodiment 2
Take by weighing Zulkovsky starch 20.00g, join (100ml) in the small beaker that contains the 30ml deionized water, stir into pasty state with glass stick.Take by weighing 1.00g Fe (NO again
3)
39H
2O also is dissolved in it in 50ml deionized water, and slowly adding a mole dosage ratio in this solution is the NaOH of 3: 1 0.1mol/L, generates Fe (OH)
3Precipitation is with Fe (OH)
3Precipitation joins in the above-mentioned starch paste, obtains the brown paste after fully stirring, and puts into baking oven dry 2h under 100 ℃, with mortar the exsiccant sample is ground to form fine powder.
The above-mentioned fine powder of 1.00g is put into quartz boat, place the central authorities of the crystal reaction tube (diameter 30mm, length 600mm) of tubular type charring furnace then, feed hydrogen (20cm to reaction tubes thereupon
3/ min), the speed with 5 ℃/min is warmed up to 300 ℃ with charring furnace then, and constant temperature 1h, with the temperature rise rate of 10 ℃/min charring furnace is heated to 900 ℃ from 300 ℃ again, and constant temperature 4h.After carbonization reaction stops, stopping logical hydrogen, with nitrogen with 50cm
3/ min speed feeds in the reaction tubes, and system is cooled to room temperature under nitrogen protection.Take out quartz boat, obtain the ferrum nano material that a large amount of carbon coats.
Embodiment 3
Take by weighing Zulkovsky starch 20.00g, add in the small beaker that contains the 30ml deionized water (100ml), stir into pasty state with glass stick.Take by weighing 1.00g Fe (NO again
3)
39H
2O joins in the deionized water of 50ml, and slowly adding mole dosage ratio subsequently is the NaOH of 3: 1 0.1mol/L, generates Fe (OH)
3Precipitation is with Fe (OH)
3Precipitation adds in the above-mentioned starch paste, obtains the brown paste after fully stirring, and puts into baking oven dry 2h under 100 ℃, with mortar the exsiccant sample is ground to form fine powder.
The above-mentioned fine powder of 2.00g is put into quartz boat, place the central authorities of the crystal reaction tube (diameter 30mm, length 600mm) of tubular type charring furnace then.Follow hydrogen with 20cm
3The flow rate of/min is passed into reaction tubes, with the speed of 7.5 ℃/min charring furnace is warmed up to 900 ℃ and constant temperature 4h; After carbonization reaction finishes, stop logical hydrogen, with nitrogen with 50cm
3The flow rate of/min feeds in the reaction tubes, makes system be cooled to room temperature under nitrogen protection.Take out quartz boat, obtain the ferrum nano material that a large amount of carbon coats.
Claims (4)
1, a kind of is the method that matrix prepares the carbon-coated nano metallic substance with biomaterial-starch, comprises two main processes, the one, and the preparation of charing presoma-starch and metal oxide compound; The 2nd, the compound of the starch that obtains and metal oxide is carried out charing handle under the controlled condition of gentleness, it is characterized in that concrete processing step is:
Take by weighing Zulkovsky starch 20.00g, add in the small beaker that contains the 5ml deionized water (50ml), stir into pasty state with glass stick; Take by weighing 1.00g Fe (NO
3)
39H
2O also is dissolved in it in 50ml deionized water, and slowly adding a mole dosage ratio in this solution is the NaOH of 3: 1 0.1mol/L, obtains Fe (OH)
3Throw out is again with Fe (OH)
3Throw out joins in the above-mentioned starch paste, obtains the brown paste after fully stirring, and puts into baking oven in 100 ℃ of dry 2h down, and it is standby with mortar dried sample to be ground into fine powder;
(2) the compound powder of a certain amount of starch metal oxide is put into quartz boat, then quartz boat is placed the central authorities of the crystal reaction tube in the tubular type charring furnace, with hydrogen with 20cm
3The speed of/min feeds reaction tubes, and flow is 20～50cm
3/ min, the speed with 5～10 ℃/min under hydrogen atmosphere is warmed up to 800～950 ℃ with charring furnace, and is incubated 1～4h;
(3) after carbonization reaction finishes, hydrogen is switched to nitrogen, speed is 50cm
3/ min makes reaction system be cooled to room temperature under nitrogen protection, and a large amount of black carbides that generate in quartz boat are the carbon-clad metal nano material.
2, according to claim 1 a kind of be the method that matrix prepares the carbon-coated nano metallic substance with biomaterial-starch, it is characterized in that described metal oxide compound is iron nitrate, iron(ic) chloride, Xiao Suangu and single nickel salt.
3, according to claim 1 a kind of be the method that matrix prepares the carbon-coated nano metallic substance with biomaterial-starch, it is characterized in that, described charring furnace is heated up, make hydrogen be warmed up to 900 ℃, and constant temperature 4h with the speed of 5-10 ℃/min.
4, according to claim 1 a kind of be the method that matrix prepares the carbon-coated nano metallic substance with biomaterial-starch, it is characterized in that the diameter of described crystal reaction tube is 30mm, length is 600mm.
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|---|---|---|---|
| CN 200310119200 CN1241705C (en) | 2003-12-21 | 2003-12-21 | Method for preparing carbon-coated nano metal material by using biological material-starch as matrix |
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|---|---|---|---|
| CN 200310119200 CN1241705C (en) | 2003-12-21 | 2003-12-21 | Method for preparing carbon-coated nano metal material by using biological material-starch as matrix |
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|---|---|
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| CN1241705C CN1241705C (en) | 2006-02-15 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970575B (en) * | 2006-11-30 | 2010-05-12 | 华南理工大学 | Process for preparing superparamagnetic starch |
| CN101176915B (en) * | 2006-11-09 | 2010-05-26 | 南京大学 | Method for preparing nano metallic nickel granular material coating with carbon |
| CN102136333A (en) * | 2011-01-18 | 2011-07-27 | 大连理工大学 | Method for preparing quasi-annular magnetic carbon microsphere from starch |
| CN101728526B (en) * | 2009-12-09 | 2011-11-09 | 北京化工大学 | Lithium ion battery cathode material and preparation method thereof |
| CN102456871A (en) * | 2010-10-29 | 2012-05-16 | 新疆大学 | Preparation method of lithium-ion battery anode materials using flocculant as carbon source |
| CN102806356A (en) * | 2012-07-30 | 2012-12-05 | 西安科技大学 | Preparation method of carbon-coated copper nanoparticles with core-shell structures |
| CN105125499A (en) * | 2015-09-24 | 2015-12-09 | 何孝隆 | Preparation process of interventional therapy magnetic targeting drug carrier |
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| CN109294600A (en) * | 2018-12-06 | 2019-02-01 | 黑龙江省能源环境研究院 | A kind of more storehouse vertical type biomass carbonization experimental furnace and its application method |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176915B (en) * | 2006-11-09 | 2010-05-26 | 南京大学 | Method for preparing nano metallic nickel granular material coating with carbon |
| CN1970575B (en) * | 2006-11-30 | 2010-05-12 | 华南理工大学 | Process for preparing superparamagnetic starch |
| CN101728526B (en) * | 2009-12-09 | 2011-11-09 | 北京化工大学 | Lithium ion battery cathode material and preparation method thereof |
| CN102456871A (en) * | 2010-10-29 | 2012-05-16 | 新疆大学 | Preparation method of lithium-ion battery anode materials using flocculant as carbon source |
| CN102136333A (en) * | 2011-01-18 | 2011-07-27 | 大连理工大学 | Method for preparing quasi-annular magnetic carbon microsphere from starch |
| CN102136333B (en) * | 2011-01-18 | 2013-05-08 | 大连理工大学 | Method for preparing quasi-annular magnetic carbon microsphere from starch |
| CN102806356A (en) * | 2012-07-30 | 2012-12-05 | 西安科技大学 | Preparation method of carbon-coated copper nanoparticles with core-shell structures |
| CN102806356B (en) * | 2012-07-30 | 2014-12-17 | 西安科技大学 | Preparation method of carbon-coated copper nanoparticles with core-shell structures |
| CN105125499A (en) * | 2015-09-24 | 2015-12-09 | 何孝隆 | Preparation process of interventional therapy magnetic targeting drug carrier |
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