CN105655078B - Magnetic composite with nucleocapsid and preparation method thereof - Google Patents
Magnetic composite with nucleocapsid and preparation method thereof Download PDFInfo
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- CN105655078B CN105655078B CN201410646156.7A CN201410646156A CN105655078B CN 105655078 B CN105655078 B CN 105655078B CN 201410646156 A CN201410646156 A CN 201410646156A CN 105655078 B CN105655078 B CN 105655078B
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 113
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011859 microparticle Substances 0.000 claims abstract description 52
- 229940056319 ferrosoferric oxide Drugs 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
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- Hard Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention discloses a kind of magnetic composites with nucleocapsid and preparation method thereof, the magnetic composite of the present invention is made of the shell that Fe 3 O 4 magnetic core and silica are formed, wherein, the shell coated ferroferric oxide magnetic core that silica is formed, the Fe 3 O 4 magnetic core is the aggregate of single ferroso-ferric oxide micro particles or the ferroso-ferric oxide micro particles for being 2 or more.The magnetic composite with nucleocapsid of the present invention is easy to industrial production, has good chemical stability, and still have higher magnetism under the high temperature conditions.
Description
Technical field
The present invention relates to a kind of magnetic composites with nucleocapsid and preparation method thereof.
Background technology
Ferrite Material magnetic performance is good, and preparation process is simple, and manufacturing cost is low.Nanometer ferrite especially nanometer Fe3O4
For material in coating, the application prospects of biology and medicine and other fields are fine.But due to nano-ferrite material thermodynamic instability,
The shortcomings of with poor chemical stability, being easily oxidised, being easy to react with acid, seriously hinders its extensive use.To ferrite
Material is surface modified (such as to be carried by surfactants such as chemisorbed and chemisorbed dodecyl sodium sulfate, enuatrols
Its high stability) and coat (as using macromolecules and SiO such as glucose, chitosan, polyethylene glycol, polyvinyl alcohol, polylactic acid2
Wait inorganic matters) it is the effective means for improving its stability.SiO2It can be formed on nano-ferrite material surface continuous without fixed
The clad of shape.The inertia clad of formation can effectively improve protection encapsulated material, improve its chemical stability.Together
When, due to SiO2Material surface has abundant group, is easy to be surface modified the expansion with function.
In United States Patent (USP) US2013/0342069A1 (patent publication No.) SiO is prepared for using coprecipitation method2Cladding
Monokaryon Fe3O4Nanocomposite.Product grain diameter is less than 50 nanometers.But its saturation magnetization is smaller, and only 1emu is left
It is right.
Ferrite nano particles are prepared using coprecipitation method in CN1477082A, later using inorganic silicon source and organosilicon
Source carries out secondary cladding to particle, and the nano-particle of grain size 500-200 is prepared.
CN1594450A discloses a kind of SiO2The nanometer Fe composite material of cladding using organic acid is complexing in this application
Agent, using ethyl orthosilicate as silicon source, using H2Reduction obtains the composite particles less than 10 nanometers.The material is less than 150 in temperature
DEG C when it is more stable, but higher than the temperature when, be easily oxidised and lose magnetism in air.
The compound iron oxygen that CN1459433A is prepared for having nucleocapsid by secondary coating method in water phase and organic phase
Body magnetic material, and the composite magnetic is modified using silylating reagent.The wherein a diameter of 5-8 of kernel ferrite
Nanometer.
CN 103500622A report a kind of magnetic inorganic nanoparticle/amorphous silica/sky of ordered mesoporous pore canals
Chamber/ordered meso-porous silica core-shell complex microsphere.This complex microsphere is used for medical diagnosis.
Also, in the above-mentioned published patent application, since nanoscale Ferrite Material size is smaller, grasped in practical preparation
Make cumbersome, condition harshness, even if carrying out SiO2After cladding formation meets material, in actual use, separating difficulty is big, easily
In pollution products, its large-scale production and commercial Application are limited.
Invention content
The purpose of the present invention is to provide it is a kind of it is simple and quick, be easy to the industrial magnetic coupling with nucleocapsid
Material and preparation method thereof, also, the magnetic composite with nucleocapsid is somebody's turn to do with good chemical stability, in high temperature
Under the conditions of still have higher magnetism.
Present inventors discovered unexpectedly that unformed fine and close four oxidation three of shell cladding formed by silica
Ferromagnetism core, and the Fe 3 O 4 magnetic core is single ferroso-ferric oxide micro particles or four oxygen for being 2 or more
When changing the aggregate of three-iron micro particles, it is good to obtain a kind of chemical stability, and still have under the high temperature conditions compared with
The high magnetic magnetic composite with nucleocapsid, has thus completed the present invention.
That is, the present invention provides a kind of magnetic composite with nucleocapsid, wherein, the magnetic composite is by four
The shell composition that Fe 3 O magnetic core and silica are formed, wherein, the unformed fine and close shell cladding that silica is formed
Fe 3 O 4 magnetic core, the Fe 3 O 4 magnetic core is single ferroso-ferric oxide micro particles or is 2 or more
Ferroso-ferric oxide micro particles aggregate.
The present invention also provides a kind of preparation method of the magnetic composite with nucleocapsid, wherein, this method includes
Following steps：
1) ferroso-ferric oxide micro particles are carried out first with inorganic acid to contact, and is detached from the product after the first contact
Go out the ferroso-ferric oxide micro particles after contact；
2) in ethanol water, ferroso-ferric oxide micro particles and ammonium hydroxide and silicon source after the contact that step 1) is obtained
The second contact is carried out, and solid product is isolated from the product after the second contact；
3) solid product that step 2) obtains is roasted.
The present invention also provides the magnetic composites with nucleocapsid being prepared by the above method.
Magnetic composite according to the present invention with nucleocapsid passes through four oxygen of coated with silica micron level
Change three ferromagnetic particles, the chemical stability and inoxidizability of magnetic composite can not only be greatly improved, and can have
Effect ground keeps the magnetism of composite material so that it still has higher magnetism under the high temperature conditions, and can further carry out
Functionalization.
According to the present invention, due to the use of ferroso-ferric oxide micro particles as magnetic core, compared to using nano-particle as magnetic
Property core, the preparation method of ferroso-ferric oxide micro particles is simple, and ferroso-ferric oxide micro particles have been realized on a large scale
Industrial production derives from a wealth of sources so that the magnetic composite with nucleocapsid of the invention is easy to carry out industrial production.And
And it in the preparation method of the magnetic composite with nucleocapsid of the invention, can be detached by magnetic separation method, greatly
The earth reduces the difficulty of separation, is easy to carry out industrial production.
In addition, the preparation method of the magnetic composite according to the present invention with nucleocapsid, has higher packet
Cover rate.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention, but be not construed as limiting the invention together.In the accompanying drawings：
Fig. 1 is the F represented used in embodiment 13O4The figure of the Malvern laser particle size analysis result of particle；
Fig. 2 is the F used in embodiment 13O4Transmission electron microscope (TEM) photo of particle；
Fig. 3 is the TEM photos of the magnetic composite A1 with nucleocapsid that embodiment 1 obtains；
Fig. 4 is the F used in embodiment 13O4Scanning electron microscope (SEM) photo of particle；
Fig. 5 is the SEM photograph of the magnetic composite A1 with nucleocapsid that embodiment 1 obtains；
Fig. 6 is the hysteresis loop of the magnetic composite A1 with nucleocapsid that embodiment 1 obtains；
Fig. 7 is the F used in embodiment 13O4X-ray diffraction (XRD) spectrogram after particle roasting；
Fig. 8 is the XRD spectra of the magnetic composite A1 with nucleocapsid that embodiment 1 obtains.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Magnetic composite provided by the invention with nucleocapsid is by Fe 3 O 4 magnetic core and silica shape
Into shell composition, wherein, the unformed fine and close shell coated ferroferric oxide magnetic core that silica is formed, four oxidation
Three-iron magnetic core is the reunion of single ferroso-ferric oxide micro particles or the ferroso-ferric oxide micro particles for being 2 or more
Body.
According to the present invention, in order to advanced optimize the performances such as specific saturation magnetization, preferably described Fe 3 O 4 magnetic
Core is the aggregate of the ferroso-ferric oxide micro particles of 2 or more；The more preferable Fe 3 O 4 magnetic core is 2-200 four
The aggregate of Fe 3 O micro particles；The more preferable Fe 3 O 4 magnetic core is 2-100 ferroso-ferric oxide micron grain
The aggregate of son；Aggregate of the more preferable Fe 3 O 4 magnetic core for 2-50 ferroso-ferric oxide micro particles；Into one
Step preferably aggregate of the Fe 3 O 4 magnetic core for 5-50 ferroso-ferric oxide micro particles.
In the present invention, the grain size of the ferroso-ferric oxide micro particles is micron level, it is preferable that four oxygen
The grain size for changing three-iron micro particles is 1-20um；More preferably 1-15um；Further preferably 1-10um.
According to the present invention, there is no particular limitation, but for raising for the thickness of shell formed for the silica
Consider in terms of clad ratio and specific saturation magnetization, the thickness of shell that preferably described silica is formed is 0.01-
0.5um；More preferably 0.01-0.3um；Further preferably 0.02-0.25um；Still more preferably it is 0.1-0.25um.
The present invention also provides a kind of preparation method of the magnetic composite with nucleocapsid, wherein, this method includes
Following steps：
1) ferroso-ferric oxide micro particles are carried out first with inorganic acid to contact, and is detached from the product after the first contact
Go out the ferroso-ferric oxide micro particles after contact；
2) in ethanol water, ferroso-ferric oxide micro particles and ammonium hydroxide and silicon source after the contact that step 1) is obtained
The second contact is carried out, and solid product is isolated from the product after the second contact；
3) solid product that step 2) obtains is roasted.
According to the present invention, the grain size of the ferroso-ferric oxide micro particles is micron level, it is preferable that four oxygen
The grain size for changing three-iron micro particles is 1-20um；More preferably 1-15um；Further preferably 1-10um.
In accordance with the present invention it is preferred that the inorganic acid is one or more in hydrochloric acid, nitric acid and sulfuric acid；More preferably
Hydrochloric acid.
In the present invention, the concentration of the inorganic acid can change in wide range, it is preferable that the inorganic acid it is dense
It spends for 0.05-1mol/L；More preferably 0.1-1mol/L.
, according to the invention it is preferred to first contact carries out under stiring or under ultrasonic wave.
According to the present invention, first contact is used for the modification on ferroso-ferric oxide micro particles surface.The item of the contact
As long as part is so that ferroso-ferric oxide micro particles surface is fully modified.Preferably, the condition of the contact includes：Contact
Temperature is 15-85 DEG C, and the time of contact is 1 minute or more；It is highly preferred that the condition of the contact includes：The temperature of contact is
20-35 DEG C, the time of contact is 1-60 minutes.
According to the present invention, the method that the ferroso-ferric oxide micro particles after contact are isolated from the product after the first contact
Can be various methods commonly used in the art.Due to the present invention the ferroso-ferric oxide micro particles for using micron level,
It has higher magnetism.Therefore.In order to simplify step, the present invention is preferably by magnetic separation method from the product after the first contact
Isolate the ferroso-ferric oxide micro particles after contact.
In the case of, according to the invention it is preferred to, this method further includes, four oxidations three after the contact for obtaining step 1)
Before iron micro particles are contacted with ammonium hydroxide and silicon source progress second, the ferroso-ferric oxide micron grain after the contact that step 1) is obtained
Son is washed.There is no particular limitation for the solvent of the washing, such as can be ethyl alcohol and water.
According to the present invention, in step 2), the volume ratio of the second alcohol and water in the ethanol water can be 0.1-50：
1；Preferably 1-10：1.
According to the present invention, in step 2), the weight ratio of the ethanol water and ferroso-ferric oxide micro particles can be
20-500：1；Preferably 25-100：1.
According to the present invention, in step 2), the volume ratio of the ethanol water and ammonium hydroxide can be 20-100：1；Preferably
30-40：1.The concentration of the ammonium hydroxide can be 20-30 weight %；Preferably 25-28 weight %.
According to the present invention, in step 2), the silicon source can be commonly used in the art various to be used to form the siliceous of shell
Compound.Such as the silicon source can be one or more in tetraethyl orthosilicate, Ludox and potassium silicate；Preferably positive silicon
Sour tetra-ethyl ester.
According to the present invention, as long as the dosage of the silicon source can fully coat the ferroso-ferric oxide micro particles i.e.
It can.Preferably, the silicon source and the molar ratio of the ferroso-ferric oxide micro particles are 0.01-100：1；More preferably 0.1-
50：1.
According to the present invention, the condition of second contact includes：The temperature of contact is 15-85 DEG C, time of contact 0.1-
12 hours；Preferably, the condition of second contact includes：The temperature of contact is 20-35 DEG C, and time of contact is 1-10 hours
According to the present invention, the method that solid product is isolated from the product after the second contact can be commonly used in the art
Various methods.Due to the ferroso-ferric oxide micro particles for using micron level of the present invention, there is higher magnetism.Cause
This.In order to simplify step, the present invention preferably isolates solid product by magnetic separation method from the product after the second contact.
In the case of, according to the invention it is preferred to, this method further includes before the firing, and solid phase production is isolated to described
Object is washed and is dried.The solvent of the washing there is no particular limitation, it is preferable to use second contact used in solvent,
Such as second alcohol and water.Also there is no particular limitation for the method for the drying, such as can be dried 6-24 hours at 80-150 DEG C.
According to the present invention, in step 3), the temperature of the roasting can be 280-650 DEG C, and the time of roasting can be 1-6
Hour；Preferably, the temperature of the roasting is 300-500 DEG C, and the time of roasting is 2-4 hours
The present invention also provides a kind of magnetic composites with nucleocapsid obtained by the above method.
The present invention will be described in detail by way of examples below, but the present invention is not limited in following embodiments.
In following embodiment, the grain of ferroso-ferric oxide micro particles is measured by the method for Malvern laser particle size analysis
Diameter.
It is surveyed by transmission electron microscope (TEM), scanning electron microscope (SEM) and X-ray diffraction analysis (XRD) method
Surely the structure of the composite material obtained.
Clad ratio (the molten rear remaining sample quality of clad ratio=acid/rise of silica is measured by inorganic acid solution method
Beginning sample quality * 100%).
The specific saturation magnetization of the composite material measured by shaking sample magnetometer.
Embodiment 1
At 25 DEG C, the Fe of 1-10 μm of 10g grain sizes is weighed3O4Particle is placed in the 0.1molL of 1000ml-1HCl/water solution
In, after ultrasonic 10min, carry out the Fe after Magneto separate is surface-treated3O4Particle, with the ethyl alcohol of 850ml to the surface treatment after
Fe3O4Particle is washed, and is dispersed in 550ml ethyl alcohol, 150ml deionized waters and 15ml concentrated ammonia liquors (a concentration of 25 weight later
Measure %) in mixed liquor, 12.5g tetraethyl orthosilicate solution is added in, at 25 DEG C, is stirred to react 5h.Magneto separate is carried out after having reacted
Solid particle is obtained, respectively using the ethyl alcohol of 850ml and the water washing solid particle of 850ml.Then by solid particle at 120 DEG C
Dry 12h, roasts 4 hours under the conditions of 400 DEG C, obtains the magnetic composite A1 with nucleocapsid later.
Fig. 1 is the F represented used in embodiment 13O4The figure of the Malvern laser particle size analysis result of particle, can by Fig. 1
Know, Fe used in embodiment 13O4The grain size of particle is 1-10 μm；
Fig. 2 is the F used in embodiment 13O4Transmission electron microscope (TEM) photo of particle, Fig. 3 are obtained for embodiment 1
The TEM photos of the magnetic composite A1 with nucleocapsid arrived, comparison diagram 2 by Fig. 3 transmission electron microscope (TEM) table
Result is levied to understand：Magnetic composite A1 has nucleocapsid, in Fe3O4Surface forms the unformed SiO of thickness about 150nm2Packet
Coating, also, magnetic core is by 5-50 Fe3O4Particle is formed；
Fig. 4 is the F used in embodiment 13O4Scanning electron microscope (SEM) photo of particle, Fig. 5 are obtained for embodiment 1
The SEM photograph of the magnetic composite A1 with nucleocapsid arrived compares the Fe before cladding3O4Particle (Fig. 4), by scanning electricity
Sub- microscope (SEM) characterization result Fig. 5 is understood：Material surface after cladding is smooth, and grain edges and angle point are no longer prominent, more
It is mellow and full；
Fig. 6 is the hysteresis loop of the magnetic composite A1 with nucleocapsid that embodiment 1 obtains, as shown in fig. 6, point
Analyse the hysteresis loop of magnetic composite A1 tested by vibrations sample magnetometer, it is known that its specific saturation magnetization is
53.2emu/g；
Fig. 7 is the F used in embodiment 13O4(its roasting condition is X-ray diffraction (XRD) spectrogram after particle roasting
Roasted 4 hours under the conditions of 400 DEG C), the XRD spectrums that Fig. 8 is the magnetic composite A1 with nucleocapsid that embodiment 1 obtains
Figure, by the XRD spectra of Fig. 7 and Fig. 8 it is found that preparing the core of resulting materials with Fe3O4Crystal form exists, SiO2With unformed shape
Formula exists.
In addition, the clad ratio of silica is as shown in table 1.
Embodiment 2
At 25 DEG C, the Fe of 1-10 μm of 10g grain sizes is weighed3O4Particle is placed in the 1mol L of 1000ml-1HCl/water solution
In, after ultrasonic 10min, carry out the Fe after Magneto separate is surface-treated3O4Particle, with the ethyl alcohol of 850ml to the surface treatment after
Fe3O4Particle is washed, and is dispersed in 350ml ethyl alcohol, 350ml deionized waters and 35ml concentrated ammonia liquors (a concentration of 28 weight later
Measure %) in mixed liquor, 25g tetraethyl orthosilicate solution is added in, at 75 DEG C, is stirred to react 10h.Magneto separate is carried out after having reacted to obtain
To solid particle, respectively using the ethyl alcohol of 850ml and the water washing solid particle of 850ml.Then it is solid particle is dry at 120 DEG C
Dry 12h roasts 2 hours under the conditions of 500 DEG C, obtains the magnetic composite A2 with nucleocapsid later.
Based on measure identical in embodiment 1 it is found that the Fe used in embodiment 23O4The grain size of particle is 1-10 μm；Magnetic
Property composite A 2 have nucleocapsid, in Fe3O4Surface forms the unformed SiO of thickness about 250nm2Clad, and magnetic
Property core is by 20-50 Fe3O4Particle is formed；Material surface after cladding is smooth, and grain edges and angle point are no longer prominent, more round
Profit；Analyze the hysteresis loop of magnetic composite A2 tested by vibrations sample magnetometer, it is known that it is stronger than saturated magnetization
It spends for 50.5emu/g；By XRD spectra it is found that preparing the core of resulting materials with Fe3O4Crystal form exists, SiO2With unformed shape
Formula exists.
In addition, the clad ratio of silica is as shown in table 1.
Embodiment 3
At 25 DEG C, the Fe of 1-5 μm of 10g grain sizes is weighed3O4Particle is placed in the 1mol L of 1000ml-1HCl/water solution
In, after ultrasonic 10min, carry out the Fe after Magneto separate is surface-treated3O4Particle, with the ethyl alcohol of 1000ml to the surface treatment
Fe afterwards3O4Particle is washed, and is dispersed in 600ml ethyl alcohol, 60ml deionized waters and 33ml concentrated ammonia liquors (a concentration of 25 weight later
Measure %) in mixed liquor, 33g tetraethyl orthosilicate solution is added in, at 25 DEG C, is stirred to react 1h.Magneto separate is carried out after having reacted to obtain
To solid particle, respectively using the ethyl alcohol of 850ml and the water washing solid particle of 850ml.Then it is solid particle is dry at 120 DEG C
Dry 12h roasts 10 hours under the conditions of 300 DEG C, obtains the magnetic composite A3 with nucleocapsid later.
Based on measure identical in embodiment 1 it is found that the Fe used in embodiment 33O4The grain size of particle is 1-5 μm；It is magnetic
Composite A 3 has nucleocapsid, in Fe3O4Surface forms the unformed SiO of thickness about 100nm2Clad, and it is magnetic
Core is by 2-50 Fe3O4Particle is formed；Material surface after cladding is smooth, and grain edges and angle point are no longer prominent, more mellow and full；
Analyze the hysteresis loop of magnetic composite A3 tested by vibrations sample magnetometer, it is known that its specific saturation magnetization is
56.8emu/g；By XRD spectra it is found that preparing the core of resulting materials with Fe3O4Crystal form exists, SiO2It is deposited with amorphous forms
.
In addition, the clad ratio of silica is as shown in table 1.
Comparative example 1
Weigh the Fe that 1g grain sizes are 50nm3O4Particle is put into three-necked flask, adds in the deionized water of 40ml, add in 40ml without
Water-ethanol adds in the sodium dodecyl sulfate aqueous solution 30ml, 50 DEG C of stirring in water bath 30min of 0.1mol/L.Add in the ammonium hydroxide of 6ml
With the Na of 6ml2SiO3, stop stirring after reacting 3h, material D1 be dried to obtain after deionized water washing.
Based on measure identical in embodiment 1 it is found that the Fe used in comparative example 13O4The grain size of particle is 50nm；Comparison
The structure of material D1 that example obtains is nucleocapsid SiO2Coat nanometer Fe3O4；Analysis is by vibrations sample magnetometer test comparison example
The 1 obtained hysteresis loop of material D1, it is known that its specific saturation magnetization is 24.6emu/g.
In addition, the clad ratio of silica is as shown in table 1.
Table 1
| Embodiment is numbered | Clad ratio (%) |
| Embodiment 1 | 85.0 |
| Embodiment 2 | 86.7 |
| Embodiment 3 | 80.5 |
| Comparative example 1 | 36.1 |
By above-described embodiment 1 it is found that the magnetic composite A1 of the nucleocapsid of the present invention is roasted under the conditions of 400 DEG C
Material obtained from after burning 4 hours, the specific saturation magnetization of magnetic composite A1 obtained after 400 DEG C of roastings are
53.2emu/g illustrates that (such as under conditions of 400 DEG C) still have higher magnetism at high temperature for it.In addition, it combines other
Embodiment passes through silica it is found that the obtained magnetic composite of preparation method according to the invention has nucleocapsid
The Fe 3 O 4 magnetic particle of micron level is coated, the chemical stability of magnetic composite can not only be greatly improved and is resisted
Oxidisability, and the magnetism of composite material can be effectively kept so that it still has higher magnetism under the high temperature conditions.
In addition, comparative example 1 is using nanometer Fe3O4Particle prepares nucleocapsid SiO2Coat nanometer Fe3O4, do not undergoing
In the case of high temperature, specific saturation magnetization is only 24.6emu/g.It can be seen that preparation method according to the invention obtained
Magnetic composite has high chemical stability and inoxidizability, can effectively keep the magnetism of composite material, and
Still there is higher magnetism under the high temperature conditions.
Further, since the present invention can use ferroso-ferric oxide micro particles to make as magnetic core compared to nano-particle
It for magnetic core, derives from a wealth of sources so that the magnetic composite with nucleocapsid of the invention is easy to carry out industrial production.And
And it in the preparation method of the magnetic composite with nucleocapsid of the invention, can be detached by magnetic separation method, greatly
The earth reduces the difficulty of separation, is easy to carry out industrial production.
In addition, the preparation method of the magnetic composite according to the present invention with nucleocapsid is with higher cladding
Rate.
In addition, it can be shown that the Fe 3 O 4 magnetic core quilt of the magnetic composite of the present invention by the data of above-mentioned table 1
The shell densification cladding that silica is formed.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of magnetic composite with nucleocapsid, which is characterized in that the magnetic composite is by ferroso-ferric oxide magnetic
Property the shell composition that is formed of core and silica, wherein, the unformed fine and close shell coated ferriferrous oxide that silica is formed
Magnetic core, the Fe 3 O 4 magnetic core are the aggregate of the ferroso-ferric oxide micro particles of 2 or more, four oxidation three
The grain size of iron micro particles is 1-20um.
2. magnetic composite according to claim 1, wherein, the Fe 3 O 4 magnetic core is 2-200 four oxygen
Change the aggregate of three-iron micro particles.
3. magnetic composite according to claim 2, wherein, the Fe 3 O 4 magnetic core is 2-100 four oxygen
Change the aggregate of three-iron micro particles.
4. magnetic composite according to claim 3, wherein, the Fe 3 O 4 magnetic core is 2-50 four oxidation
The aggregate of three-iron micro particles.
5. magnetic composite according to claim 4, wherein, the Fe 3 O 4 magnetic core is 5-50 four oxidation
The aggregate of three-iron micro particles.
6. magnetic composite according to claim 1, wherein, the grain size of the ferroso-ferric oxide micro particles is 1-
15um。
7. magnetic composite according to claim 6, wherein, the grain size of the ferroso-ferric oxide micro particles is 1-
10um。
8. magnetic composite according to claim 1, wherein, the thickness for the shell that the silica is formed is
0.01-0.5um。
9. magnetic composite according to claim 8, wherein, the thickness for the shell that the silica is formed is
0.01-0.3um。
10. magnetic composite according to claim 9, wherein, the thickness for the shell that the silica is formed is
0.02-0.25um。
11. magnetic composite according to claim 10, wherein, the thickness for the shell that the silica is formed is
0.1-0.25um。
12. the preparation method of the magnetic composite with nucleocapsid described in any one in a kind of claim 1-11,
It is characterized in that, this method includes the following steps：
1) ferroso-ferric oxide micro particles are carried out first with inorganic acid to contact, and isolates and connect from the product after the first contact
Ferroso-ferric oxide micro particles after touch；
2) in ethanol water, the ferroso-ferric oxide micro particles after the contact that step 1) is obtained are carried out with ammonium hydroxide and silicon source
Second contact, and isolate solid product from the product after the second contact；
3) solid product that step 2) obtains is roasted.
13. according to the method for claim 12, wherein, the grain size of the ferroso-ferric oxide micro particles is 1-20um.
14. according to the method for claim 13, wherein, the grain size of the ferroso-ferric oxide micro particles is 1-15um.
15. according to the method for claim 14, wherein, the grain size of the ferroso-ferric oxide micro particles is 1-10um.
16. according to the method for claim 12, wherein, the inorganic acid is one kind or more in hydrochloric acid, nitric acid and sulfuric acid
Kind.
17. the method according to claim 11, wherein, a concentration of 0.05-1mol/L of the inorganic acid.
18. according to the method for claim 12, wherein, four oxidations after contact are isolated from the product after the first contact
The method of three-iron micro particles is magnetic separation method.
19. according to the method for claim 12, wherein, the condition of first contact includes：The temperature of contact is 15-85
DEG C, the time of contact is 1 minute or more.
20. the method according to claim 11, wherein, in step 2), the body of the second alcohol and water in the ethanol water
Product is than being 0.1-50：1.
21. the method according to claim 11, wherein, in step 2), the ethanol water and ferroso-ferric oxide micron
The weight ratio of particle is 20-500：1.
22. the method according to claim 20 or 21, wherein, in step 2), the volume of the ethanol water and ammonium hydroxide
Than for 20-100：1, and a concentration of 20-30 weight % of the ammonium hydroxide.
23. the method according to claim 20 or 21, wherein, in step 2), the silicon source is tetraethyl orthosilicate, silicon is molten
It is one or more in glue and potassium silicate.
24. the method according to claim 11, wherein, in step 2), the silicon source and the ferroso-ferric oxide micron grain
The molar ratio of son is 0.01-100：1.
25. according to the method for claim 12, wherein, in step 2), the condition of second contact includes：The temperature of contact
It is 15-85 DEG C to spend, and time of contact is 0.1-12 hours.
26. according to the method for claim 12, wherein, in step 2), solid phase is isolated from the product after the second contact
The method of product is magnetic separation method.
27. according to the method for claim 12, wherein, in step 3), the temperature of the roasting is 280-650 DEG C, roasting
Time be 1-6 hours.
28. a kind of magnetic composite with nucleocapsid, which is characterized in that the magnetic composite passes through claim
Method in 12-27 described in any one is prepared.
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| CN107803180B (en) * | 2017-11-15 | 2019-06-07 | 海南医学院 | A kind of order mesoporous Fe of magnetism3O4The preparation method of@MCM-48 composite adsorbing material |
| CN108231309A (en) * | 2018-01-22 | 2018-06-29 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method of magnetic silica microballoon |
| CN111499370B (en) * | 2020-05-20 | 2022-06-24 | 中国科学院重庆绿色智能技术研究院 | Preparation method of coated ferromagnetic material |
| CN115820181A (en) * | 2022-12-07 | 2023-03-21 | 东莞市新懿电子材料技术有限公司 | Underfill adhesive based on composite nano filler and preparation method and application thereof |
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