CN100463849C - Method for preparing carbon hollow ball with magnetic material filler - Google Patents
Method for preparing carbon hollow ball with magnetic material filler Download PDFInfo
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- CN100463849C CN100463849C CNB2007100717103A CN200710071710A CN100463849C CN 100463849 C CN100463849 C CN 100463849C CN B2007100717103 A CNB2007100717103 A CN B2007100717103A CN 200710071710 A CN200710071710 A CN 200710071710A CN 100463849 C CN100463849 C CN 100463849C
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Abstract
The invention relates to a manufacturing method for carbon hollow ball filed by magnetic material. It includes the following steps: mixing ferrocene 50-80wt% with ammonium chloride 20-50wt%, taking ball milling to the raw material; putting into pressure reacting furnace to take reaction; the reacted black powder would be put into deionized water to take hydrolysis after cooling; taking thermal process in tubular furnace to the product after reacting; putting the product into Buchner filter, taking washing and filtering by thick hydrochloric acid to gain carbon hollow ball containing magnetic material. The invention has the advantages of low cost, good repeatability, and high yield.
Description
Technical field
The present invention relates to the preparation method of carbon hollow ball.
Background technology
Thereby hollow ball section bar material is owing to have the physicochemical property that special hollow structure has many uniquenesses: as lower density, and certain mechanical strength, big specific surface area, excellent thermostability, perviousness etc.; And owing to be a contact, therefore be difficult for reuniting, be convenient to storage.So can be widely used in fields such as medicament storage and transport, artificial cell, lightweight structural material, damping material and support of the catalyst.Wherein carbon hollow ball has excellent biocompatibility, and is easy to finishing, make its surface have other functional groups, so carbon hollow ball has more application potential at field of medicaments.Z 250 has been widely used in scientific research and commercial field owing to have magnetic responsiveness.And test shows that it has excellent biocompatibility, harmless, so scientists is separated at target medicine carrier, cell and biological entities, human tissue engineering, magnetic resonance imaging imaging, alternating magnetic field heat to treat fields such as cancer it has been carried out broad research.But ferroferric oxide nano granules is reunited in application process easily, and erosion resistance and abrasion resistance are poor.If its inside that is filled in carbon hollow ball will effectively be addressed these problems.The medicine but also pack in the ball chamber that can utilize carbon hollow ball, the drug targeting carrier as having slow-releasing is with a wide range of applications at field of medicaments.But the research of carbon current hollow ball also is in the starting stage, and some reports about synthetic aspect are only arranged, and complex process, material toxicity higher, yield poorly, be not suitable for scale operation, seriously hindered its application process.In addition, the research about magneticsubstance filling carbon hollow ball does not appear in the newspapers yet.
Summary of the invention
The present invention is poor in order to solve ferroferric oxide nano granules reunion easily, erosion resistance and abrasion resistance in application process, and the complicated process of preparation of hollow ball, material toxicity are higher, the problem that yields poorly, be not suitable for scale operation.Propose a kind of preparation method with carbon hollow ball of magneticsubstance filling, the concrete technical scheme that addresses the above problem is as follows:
Preparation method's the step that the present invention has the carbon hollow ball that magneticsubstance fills is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour;
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder;
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, heat treatment process serves as a protection gas with argon gas or nitrogen, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 300～500 ℃, and kept 1～4 hour, obtain in the ball chamber, being filled with the carbon hollow ball of Z 250 this moment;
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate filter in the filter flask fast, after repeating 3～5 times, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of Z 250.
Preparation method's the step that the present invention has the carbon hollow ball that magneticsubstance fills is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour;
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder;
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, with argon gas or nitrogen is protection gas, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 750～1400 ℃, and kept 2～4 hours, then ferric oxide and the Z 250 in the ball chamber will further be reduced by carbon hollow ball, obtains being filled with in the ball chamber carbon hollow ball of iron simple substance;
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate fast filter go in the filter flask, repeat 3～5 times after, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of iron.
The present invention is filled in Z 250 and iron simple substance in the ball chamber of carbon hollow ball, make it have excellent biocompatibility, harmless, separate at target medicine carrier, cell and biological entities, human tissue engineering, magnetic resonance imaging imaging and alternating magnetic field heat to treat fields such as cancer and be widely used.Carbon hollow ball preparation technology is simple, cost is low, good reproducibility, productive rate height.Be suitable for suitability for industrialized production.
Embodiment
Embodiment one: the step of present embodiment method is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour; Iron that produces by the ferrocene cracking in this process and ammonium chloride reaction generate the iron ammonium complex compound as liquid spherical template, the carbon atom that the cracking of surface adsorption ferrocene produces, thereby generate the carbon hollow ball that is filled with the iron ammonium complex compound in the ball chamber, wherein the external diameter of carbon hollow ball is at 1～10 μ m.
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder; This process is utilized slow the oozing property of carbon hollow ball, and water is penetrated among the ball chamber of carbon hollow ball, and makes the abundant hydrolysis of iron ammonium complex compound in the ball chamber, generates ferrous hydroxide (Fe (OH)
2), and owing to be dissolved with oxygen in the water, ferrous hydroxide will progressively be oxidized to iron oxide yellow (FeOOH), meanwhile, ferrous hydroxide will generate the Z 250 (Fe with magnetic with the iron oxide yellow reaction
3O
4) particle, because the oxidation rate of ferrous hydroxide is very fast, therefore generates excessive iron oxide yellow and also will decompose the very weak ferric oxide (α-Fe of a part of magnetic of generation
2O
3) particle.
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, heat treatment process serves as a protection gas with argon gas or nitrogen, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 300～500 ℃, and kept 1～4 hour, obtain in the ball chamber, being filled with the carbon hollow ball of Z 250 this moment; This step is utilized the reductibility of carbon hollow ball, makes oxidation and be present in a part of ferric oxide (α-Fe in the hollow ball ball chamber in hydrolytic process
2O
3) particle is converted into Z 250.
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate filter in the filter flask fast, after repeating 3～5 times, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of Z 250.This process purpose is to remove owing to damaged some Z 250s and the ferric oxide particles that causes outside ball of hollow ball; Guarantee that remaining Z 250 and ferric oxide particles are all in the ball chamber of carbon hollow ball.
Embodiment two: the step of present embodiment method is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour; Iron that produces by the ferrocene cracking in this process and ammonium chloride reaction generate the iron ammonium complex compound as liquid spherical template, the carbon atom that the cracking of surface adsorption ferrocene produces, thereby generate the carbon hollow ball that is filled with the iron ammonium complex compound in the ball chamber, wherein the external diameter of carbon hollow ball is at 1～10 μ m.
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder; This process is utilized slow the oozing property of carbon hollow ball, and water is penetrated among the ball chamber of carbon hollow ball, and makes the abundant hydrolysis of iron ammonium complex compound in the ball chamber, generates ferrous hydroxide (Fe (OH)
2), and owing to be dissolved with oxygen in the water, ferrous hydroxide will progressively be oxidized to iron oxide yellow (FeOOH), meanwhile, ferrous hydroxide will generate the Z 250 (Fe with magnetic with the iron oxide yellow reaction
3O
4) particle, because the oxidation rate of ferrous hydroxide is very fast, therefore generates excessive iron oxide yellow and also will decompose the very weak ferric oxide (α-Fe of a part of magnetic of generation
2O
3) particle.
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, with argon gas or nitrogen is protection gas, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 750～1400 ℃, and kept 2～4 hours, then ferric oxide and the Z 250 in the ball chamber will further be reduced by carbon hollow ball, obtains being filled with in the ball chamber carbon hollow ball of iron simple substance;
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate fast filter go in the filter flask, repeat 3～5 times after, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of iron.
Embodiment three: the difference of present embodiment and embodiment one is, step 1, ferrocene and ammonium chloride are pressed mass ratio 4:3 mix, totally 70 restrain, step 2, be put in urethane liner mill jar or the plastic barrel, adding Ceramic Balls or agate ball are done as abrading-ball and are mixed, and mixing time is 2 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 30 ℃ of per minutes is warming up to 550 ℃ then, and this moment, gaseous tension was 2.6MPa, and was incubated 4 hours; Furnace cooling, is put into deionized water with the gained black powder and was stirred 1 hour step 4 under air atmosphere; Step 5, be placed in the tube furnace, under the argon gas stream of 50sccm, be warming up to 500 ℃ with the speed of 10 ℃ of per minutes, and be incubated 1 hour obtaining black powder after the hydrolysis treatment; Step 6, the black powder that obtains after the thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 3 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 16 grams that Z 250 is filled.
Embodiment four: the difference of present embodiment and embodiment one is, step 1, ferrocene and ammonium chloride are pressed mass ratio 5:3 mix, totally 64 restrain, step 2, be put in urethane liner mill jar or the plastic barrel, adding Ceramic Balls or agate ball are done as abrading-ball and are mixed, and mixing time is 8 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into nitrogen to 1.9MPa, the speed with 20 ℃ of per minutes is warming up to 600 ℃ then, and this moment, gaseous tension was 2.8MPa, and was incubated 3 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 24 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put into tube furnace, under the argon gas stream of 100sccm, be warming up to 400 ℃ with the speed of 20 ℃ of per minutes, and be incubated 3 hours; Step 6, the black powder of thermal treatment gained is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 4 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 15 grams that Z 250 is filled.
Embodiment five: the difference of present embodiment and embodiment one is, step 1, ferrocene and ammonium chloride are pressed mass ratio 2:1 mixes, totally 60 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 12 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 10 ℃ of per minutes is warming up to 700 ℃ then, and this moment, gaseous tension was 3.0MPa, and was incubated 0.5 hour, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 48 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the stream of nitrogen gas of 100sccm, is warming up to 300 ℃ with the speed of 10 ℃ of per minutes, and is incubated 4 hours; Step 6, thermal treatment gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 5 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 12 grams that Z 250 is filled.
Embodiment six: the difference of present embodiment and embodiment two is, step 1, ferrocene and ammonium chloride are pressed mass ratio 2:1 mixes, totally 60 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 12 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 10 ℃ of per minutes is warming up to 700 ℃ then, and this moment, gaseous tension was 3.0MPa, and was incubated 3.0 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 30 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the stream of nitrogen gas of 100sccm, is warming up to 1200 ℃ with the speed of 10 ℃ of per minutes, and is incubated 2 hours; Step 6, the gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 4 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 10 grams that iron simple substance is filled.
Embodiment seven: the difference of present embodiment and embodiment two is, step 1, ferrocene and ammonium chloride are pressed mass ratio 5:3 mixes, totally 64 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 8 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 20 ℃ of per minutes is warming up to 600 ℃ then, and this moment, gaseous tension was 2.8MPa, and was incubated 3 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 40 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the argon gas stream of 100sccm, is warming up to 900 ℃ with the speed of 20 ℃ of per minutes, and is incubated 4 hours; Step 6, the gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 5 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 11 grams that iron simple substance is filled.
Claims (7)
1. have the preparation method of the carbon hollow ball of magneticsubstance filling, it is characterized in that this preparation method's step is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour;
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder;
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, heat treatment process serves as a protection gas with argon gas or nitrogen, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 300～500 ℃, and kept 1～4 hour, obtain in the ball chamber, being filled with the carbon hollow ball of Z 250 this moment;
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate filter in the filter flask fast, after repeating 3～5 times, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of Z 250.
2. the preparation method with carbon hollow ball of magneticsubstance filling according to claim 1, it is characterized in that step 1, ferrocene and ammonium chloride are mixed by mass ratio 4:3, totally 70 restrain, step 2, be put in urethane liner mill jar or the plastic barrel, adding Ceramic Balls or agate ball are done as abrading-ball and are mixed, and mixing time is 2 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 30 ℃ of per minutes is warming up to 550 ℃ then, and this moment, gaseous tension was 2.6MPa, and was incubated 4 hours; Furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 1 hour under air atmosphere; Step 5, be placed in the tube furnace, under the argon gas stream of 50sccm, be warming up to 500 ℃ with the speed of 10 ℃ of per minutes, and be incubated 1 hour obtaining black powder after the hydrolysis treatment; Step 6, the black powder that obtains after the thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 3 times after, with washed with de-ionized water and filter, promptly obtain containing carbon hollow ball 16 grams that Z 250 is filled in the ball chamber.
3. the preparation method with carbon hollow ball of magneticsubstance filling according to claim 1, it is characterized in that step 1, ferrocene and ammonium chloride are mixed by mass ratio 5:3, totally 64 restrain, step 2, be put in urethane liner mill jar or the plastic barrel, adding Ceramic Balls or agate ball are done as abrading-ball and are mixed, and mixing time is 8 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into nitrogen to 1.9MPa, the speed with 20 ℃ of per minutes is warming up to 600 ℃ then, and this moment, gaseous tension was 2.8MPa, and was incubated 3 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 24 hours under air atmosphere; Step 5, again the black powder that obtains after the hydrolysis treatment is put into tube furnace, under the argon gas stream of 100sccm, be warming up to 400 ℃ with the speed of 20 ℃ of per minutes, and be incubated 3 hours; Step 6, again the black powder of thermal treatment gained is put into B at last, under reduced pressure with 37% hydrochloric acid washing and filtering, after repeating 4 times,, promptly obtain containing carbon hollow ball 15 grams of Z 250 filling in the ball chamber with washed with de-ionized water and filtration.
4. the preparation method with carbon hollow ball of magneticsubstance filling according to claim 1 is characterized in that step 1, ferrocene and ammonium chloride is mixed by mass ratio 2:1, totally 60 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 12 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 10 ℃ of per minutes is warming up to 700 ℃ then, and this moment, gaseous tension was 3.0MPa, and was incubated 0.5 hour, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 48 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the stream of nitrogen gas of 100sccm, is warming up to 300 ℃ with the speed of 10 ℃ of per minutes, and is incubated 4 hours; Step 6, thermal treatment gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 5 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 12 grams that Z 250 is filled.
5. have the preparation method of the carbon hollow ball of magneticsubstance filling, it is characterized in that this preparation method's step is as follows:
Step 1, to select ferrocene and ammonium chloride for use be raw material, and ferrocene is 50%～80% by mass percentage, ammonium chloride is 20%～50%;
Step 2, the raw material uniform mixing of step 1 is prepared, put into urethane liner mill jar or plastic barrel, add to be put into to do on the ball mill behind Ceramic Balls or the agate ball and mixed 2～12 hours;
Step 3, will put into the air pressure Reaktionsofen through the uniform powder of step 2 mixing and ball milling and react, protective atmosphere is argon gas or nitrogen, charging into air pressure is 1.2～3.0MPa, temperature rise rate is 10～30 ℃ of per minutes, temperature in the stove is controlled to be 550～700 ℃, and soaking time is 0.5～4.0 hour;
Step 4, the black powder that step 3 is obtained after air pressure Reaktionsofen cooling are put into the deionized water hydrolysis under air atmosphere, and stir 1～48 hour, make the abundant hydrolysis after-filtration of iron ammonia complex in the powder;
Step 5, the black powder that obtains after the step 4 hydrolysis treatment is put into tube furnace heat-treat, with argon gas or nitrogen is protection gas, gas flow is 50～500sccm, speed with 10～30 ℃ of per minutes heats up, temperature is controlled at 750～1400 ℃, and kept 2～4 hours, then ferric oxide and the Z 250 in the ball chamber will further be reduced by carbon hollow ball, obtains being filled with in the ball chamber carbon hollow ball of iron simple substance;
Step 6, the black powder that obtains after the step 5 thermal treatment is put in the B, under reduced pressure with 37% hydrochloric acid washing and filtering, make filtrate fast filter go in the filter flask, repeat 3～5 times after, with washed with de-ionized water and filtration, promptly obtain filling in the ball chamber carbon hollow ball of iron.
6. the preparation method with carbon hollow ball of magneticsubstance filling according to claim 5 is characterized in that step 1, ferrocene and ammonium chloride is mixed by mass ratio 2:1, totally 60 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 12 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 10 ℃ of per minutes is warming up to 700 ℃ then, and this moment, gaseous tension was 3.0MPa, and was incubated 3.0 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 30 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the stream of nitrogen gas of 100sccm, is warming up to 1200 ℃ with the speed of 10 ℃ of per minutes, and is incubated 2 hours; Step 6, the gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 4 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 10 grams that iron simple substance is filled.
7. the preparation method with carbon hollow ball of magneticsubstance filling according to claim 5 is characterized in that step 1, ferrocene and ammonium chloride is mixed by mass ratio 5:3, totally 64 grams; Step 2, be put in urethane liner mill jar or the plastic barrel, add Ceramic Balls or agate ball and do mixedly as abrading-ball, mixing time is 8 hours; Step 3, the powder that mixes is placed directly in the air pressure Reaktionsofen, charges into argon gas to 1.9MPa, the speed with 20 ℃ of per minutes is warming up to 600 ℃ then, and this moment, gaseous tension was 2.8MPa, and was incubated 3 hours, furnace cooling; Step 4, the gained black powder is put into deionized water and stirred 40 hours under air atmosphere; Step 5, the black powder that obtains after the hydrolysis treatment is put in the tube furnace, under the argon gas stream of 100sccm, is warming up to 900 ℃ with the speed of 20 ℃ of per minutes, and is incubated 4 hours; Step 6, the gained black powder is put into B, under reduced pressure with 37% hydrochloric acid washing and filtering, repeat 5 times after, with washed with de-ionized water and filter, promptly obtain the ball chamber and contain carbon hollow ball 11 grams that iron simple substance is filled.
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| CN100591615C (en) * | 2008-05-20 | 2010-02-24 | 厦门大学 | Aminated magnetic carbon tube and its preparation method and application thereof in biosensor |
| CN101486491B (en) * | 2009-02-25 | 2011-01-05 | 厦门大学 | Hydroxy and amino functionalized echinus-like carbon coated ferriferrous oxide material and preparation thereof |
| CN101486455B (en) * | 2009-02-25 | 2011-01-05 | 厦门大学 | Hydroxy and amino functionalized hollow carbon nanosphere and preparation thereof |
| CN107406257A (en) * | 2015-03-11 | 2017-11-28 | 西安交通大学 | Porous carbon hollow ball and its preparation method and application |
| CN105271428B (en) * | 2015-09-30 | 2017-10-31 | 西北工业大学 | The method that pyrolytic ferrocene prepares monodisperse, ultra paramagnetic ferric oxide nano particles |
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| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| US6827919B1 (en) * | 1997-08-04 | 2004-12-07 | Hyperion Catalysis International, Inc. | Process for producing single wall nanotubes using unsupported metal catalysts and single wall nanotubes produced according to this method |
| CN1821068A (en) * | 2006-03-15 | 2006-08-23 | 哈尔滨工业大学 | Carbon hollow ball with ferrocene and ammonium chloride as raw material and its prepn |
| CN1868868A (en) * | 2006-06-09 | 2006-11-29 | 清华大学 | Method of in-situ filling symbiotic iron nanometer wire on thin wall nanometer pipe |
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2007
- 2007-01-31 CN CNB2007100717103A patent/CN100463849C/en not_active Expired - Fee Related
Patent Citations (4)
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|---|---|---|---|---|
| US6827919B1 (en) * | 1997-08-04 | 2004-12-07 | Hyperion Catalysis International, Inc. | Process for producing single wall nanotubes using unsupported metal catalysts and single wall nanotubes produced according to this method |
| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| CN1821068A (en) * | 2006-03-15 | 2006-08-23 | 哈尔滨工业大学 | Carbon hollow ball with ferrocene and ammonium chloride as raw material and its prepn |
| CN1868868A (en) * | 2006-06-09 | 2006-11-29 | 清华大学 | Method of in-situ filling symbiotic iron nanometer wire on thin wall nanometer pipe |
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| 催化裂解C2H2制备空心碳球. 许宗祥等.物理化学学报，第19卷第11期. 2003 |
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