CN104979061B - Preparation method of straight hole channel magnetic material - Google Patents
Preparation method of straight hole channel magnetic material Download PDFInfo
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- CN104979061B CN104979061B CN201410146491.0A CN201410146491A CN104979061B CN 104979061 B CN104979061 B CN 104979061B CN 201410146491 A CN201410146491 A CN 201410146491A CN 104979061 B CN104979061 B CN 104979061B
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Abstract
The present invention discloses a preparation method of a straight hole channel magnetic material. The method comprises: first, freezing and drying silica sol directionally, and then, obtaining a straight hole channel silica bulk material after high temperature calcination; next, dipping the silica bulk in FeCl3, and taking out the substance for drying; and finally, reducing the dipped and dried silica bulk by using NaBH4 or H2, so as to obtain the straight hole channel magnetic bulk material. The method is simple and easy to implement. A finished product prepared by the method has a controllable structure and good stability and can be mass-produced. Compared with a conventional porous material, the magnetic material prepared by the method has an excellent straight hole channel structure, facilitating the material transmission in the hole channel, namely; and a hole structure has small motion resistance, so permeation resistance is reduced, and efficiency is increased.
Description
Technical field
The present invention relates to a kind of preparation method of straight hole road magnetic composite.
Background technology
In recent years, porous magnetic material because of its unique structure, function and is widely applied and receives numerous concerns.Cause
This, design and produce porous magnetic material very urgent.Pore structure due to porous material is closely related with material property, because
And the control to pore structure is most important.For example, a kind of magnetic silica material with meso-hole structure is widely used
In the direction such as targeted drug transmission and multi-phase separation.A kind of with granules of polystyrene and three copolymer phases as template, by macropore, in
The Novel layered porous magnetic composite of hole and aperture composition has been used for fixed fat enzyme to be catalyzed ester hydrolysis.
There is the material of straight pore passage structure as a kind of unique porous material, in liquid chromatography, catalytic reaction and axle
The aspects such as prominent regeneration have potential using value.For example straight hole structure can be by improving the diffusion speed of gas or solute molecule
Spend and to accelerate reaction process etc..These straight pore passage structures can affect mechanical property, chemical property and the biology of material
Performance etc..
The method preparing straight hole road magnetic material at present mainly has template or self-assembling method, but for template
Method, needs to remove template last, is readily incorporated impurity；Self-assembling method process is loaded down with trivial details, is unfavorable for industrialized production, and institute
, than relatively thin or thin-film material, such material load is limited in one's ability for the material of preparation；Sample changeableness ruptures；Produce in enormous quantities
There is certain difficulty.
Content of the invention
The purpose of the present invention is exactly to solve the above problems, and provides a kind of preparation method of straight hole road magnetic material, it
Have the advantages that simple to operate, be easy to industrialized production.
For solving above-mentioned technical problem, the present invention is achieved through the following technical solutions:
A kind of preparation method of straight hole road magnetic material, comprises the following steps:
(1) will be uniform with the aqueous solution of polyvinyl alcohol (pva) and sodium lauryl sulphate (sds) for Nano silica sol,
Described pva concentration is 2.5-5wt%, and sds concentration is 0.3-0.7g/ml, and thickness of silica gel is 38-45wt%, prepared nano silicasol
Glue dispersion liquid；
(2) dispersion liquid that step (1) is obtained freezes as solid-state in liquid nitrogen；
(3) the solid dispersion liquid obtaining step (2) puts into the vacuum lyophilization that cryogenic temperature has reached -55-65 DEG C
In machine, open vacuum mode, vacuum freeze drier is in vacuum freezing mode 45-50h；
(4) sample preparing step (3) is placed in crucible, puts into calcining in resistance furnace, is warming up to 2-8 DEG C/min
800-900 DEG C, stop heating after insulation 0.5-1.5 hour, naturally cool to room temperature, obtain straight hole road silicon dioxide block；
(5) the silicon dioxide block preparing step (4) is immersed in the fecl of 0.5-2m3In solution, extracting vacuum, pressurize
Take out sample after 30min, behind washes of absolute alcohol surface, be placed in baking oven, at 80-110 DEG C, 1-1.5h be dried；
(6) concentration is the nabh of 0.1m4Solution or h2The sample that step (5) is obtained carries out reducing 0.5h, obtains
To straight hole road magnetic coupling block materials.
When with h2During reduction, reduction temperature is 500-700 DEG C, is incubated 2-4h.
Use nabh4Recovery time is 20-40min.
Straight hole road magnetic material obtained by any of the above-described preparation method.
Application in liquid chromatograph, catalytic reaction and axonal reaction for the straight hole road magnetic material obtained by said method.
The invention has the advantages that:
1. the method does not need template and purification of samples to process, and process is simple and convenient, does not have the operating procedure of complexity, freezing
It is dried, dipping and high-temperature process etc. all easily operate, the condition for preparation does not have the requirement of harshness it is easy to control yet
System；Used in preparation process, instrument is also easier to obtain, and is commercially available the relevant device meeting production in enormous quantities, easily
Large-scale production.
2. magnetic material the method being obtained preserves 1-2 month under vacuum, and the color of sample and pattern do not have
Significantly change, and still there is good magnetic.
3. can be by the control to dipping process, the concentration of such as impregnation liquid, dip time and number of times；And straight hole road
Structure of silicon dioxide etc. the structure of straight hole road magnetic material is controlled.Both only needed the change to preparation technology parameter
Different products can be obtained, greatly improve the efficiency of preparation.
4. by the method be obtained straight hole road magnetic material be used as porous material, in liquid chromatography, catalytic reaction and
The aspects such as axon regeneration have potential using value, the magnetic material compared with traditional porous material, prepared by this method
There is good straight pore passage structure, transmission in duct for the material can be conducive to, that is, little in the resistance of motion of pore structure, permissible
Reduce osmotic resistance, improve efficiency etc..
Brief description
The straight hole road magnetic silicon oxide that Fig. 1 obtains for embodiment 1 preserves 2 months pictures in front and back under vacuum；
Fig. 2 obtains the micro-structure diagram of straight hole road magnetic silicon oxide for embodiment 1 sodium borohydride reduction；
Fig. 3 obtains the corresponding enlarged drawing of microstructure of straight hole road magnetic silicon oxide for embodiment 1 sodium borohydride reduction；
Fig. 4 is the energy spectrum analysis figure of the magnetic oxygenated silicon materials in straight hole road of embodiment 1；
Fig. 5 is the micro-structure diagram of the straight hole road magnetic silicon oxide that embodiment 2 obtains；
Fig. 6 is the micro-structure diagram of the straight hole road magnetic silicon oxide that embodiment 4 obtains；
Fig. 7 is the micro-structure diagram of the straight hole road magnetic silicon oxide that embodiment 5 obtains；
Fig. 8 is the straight hole road magnetic material hysteresis curve at room temperature of embodiment 1 preparation.
Specific embodiment
It is intended to further illustrate the present invention with reference to embodiments.
Embodiment 1
Measure the pva solution of 6ml5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 800 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 0.5m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Dried sample is immersed in 30min in the nabh4 solution of 0.1m, after taking-up is cleaned with water
Obtain straight hole road magnetic coupling block materials.
When the solution containing silica nano particle is slowly immersed in liquid nitrogen, ice crystal starts along certain direction life
Long.With the oriented growth of ice crystal, silica nano particle and polyvinyl alcohol molecule are gradually disengaged and recombinate.Ice crystal is cold
Gradually distil during lyophilizing is dry, finally obtain that there is the composite porous of straight hole road.In order to obtain porous magnetic oxidation
Silicon materials, will be calcined to the composite after lyophilization to remove macromolecular polymer.
Calcining heat can produce impact to the microstructure of straight hole road porous material and mechanical performance.When calcining heat is low
When 800 DEG C, the intensity of resulting materials and toughness are all poor.This is due to, during calcining, occurring after silica nano particle sintering
Fusing, thus smaller hole is formed on hole wall.Relatively low calcining heat leads to that between atom, combination power is weaker, makes
The strength of materials declines.In this experiment, select the 800-900 DEG C of calcining heat as porous material.
Silicon dioxide is in fecl3It is in yellow after impregnating in solution, be immersed in nabh4In solution, sample is rapidly by yellow
It is changed into black, show that fe (iii) has turned into fe (0).As shown in Figure 2,3, exist in orderly passage and be made up of laminated structure
A large amount of networks.As shown in figure 4, energy spectrum analysiss understand that these networks are elementary composition by fe.
As can see from Figure 8, the hysteresis curve of this magnetic material has " s " shape, shows that this material is a class soft magnetism
Property material.
The magnetic material that the method is obtained preserves 1-2 month under vacuum, and the color of sample and pattern are not substantially
Change, and still there is good magnetic, see Fig. 1 a and Fig. 1 b.
Embodiment 2
Measure the pva solution of 6ml5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 900 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 0.5m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Dried sample is immersed in the nabh of 0.1m430min in solution, after taking-up is cleaned with water
Obtain straight hole road magnetic coupling block materials.Micro-structure diagram such as Fig. 5 of prepared straight hole road magnetic silicon oxide.
Embodiment 3
Measure the pva solution of 6ml2.5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 900 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 0.5m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Dried sample is immersed in 30min in the nabh4 solution of 0.1m, after taking-up is cleaned with water
Obtain straight hole road magnetic coupling block materials.
Embodiment 4
Measure the pva solution of 6ml5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 900 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 2.0m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Dried sample is immersed in the nabh of 0.1m430min in solution, after taking-up is cleaned with water
Obtain straight hole road magnetic coupling block materials.Micro-structure diagram such as Fig. 6 of prepared straight hole road magnetic silicon oxide.
Embodiment 5
Measure the pva solution of 6ml5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 900 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 1.0m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Control temperature at 500 DEG C, using hydrogen, sample is reduced, the recovery time is 3h, after reduction
Obtain straight hole road magnetic coupling block materials.Micro-structure diagram such as Fig. 7 of prepared straight hole road magnetic silicon oxide.
The polyhedral nano particles of fe being obtained using hydrogen reducing, this magnetic obtaining with sodium borohydride reduction more
Property material morphology different, the mechanism being primarily due to two kinds of method of reducing is different, and sodium borohydride reduction process is due to bh4 -
By fe3+It is reduced to fe0, it has very strong reducing power, leads to a large amount of nucleus in the short period of time, so in room temperature
It is down the reducible fe obtaining many lamellar network structures.And hydrogen reducing needs to carry out at high temperature, reduction process is relatively
Slowly, growing up beneficial to nucleus, finally gives polyhedron bulky grain structure.
Embodiment 6
Measure the pva solution of 6ml5wt%, add 3g sds to obtain the pva solution containing 0.5g/ml sds, with
The Ludox mixing of 6ml40wt%, is placed on magnetic stirring apparatuss, and stirring under room temperature makes Ludox dispersed in the solution.By institute
Obtain dispersion liquid to be placed in beaker and be slowly immersed in liquid nitrogen, so that dispersion liquid is freezed as solid-state.Sample after freezing is put into temperature
Reach in -60 DEG C of vacuum freeze drier, opened vacuum mode, vacuum freeze drier is in vacuum freezing mode
48h, takes out sample.Sample is placed in crucible and puts into calcining in resistance furnace, be warming up to 900 DEG C with 5 DEG C/min, stop after insulation 1h
Only heating, so as to naturally cool to room temperature in stove, obtains straight hole road silicon dioxide block.Silicon dioxide block is immersed in
The fecl of 1.0m3In aqueous solution, and extracting vacuum, take out sample after pressurize 30min, use washes of absolute alcohol surface, be placed in baking
In case, at 100 DEG C, 2h is dried.Control temperature at 700 DEG C, using hydrogen, sample is reduced, the recovery time is 3h, after reduction
Obtain straight hole road magnetic coupling block materials.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not model is protected to the present invention
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art are not
Need to pay the various modifications that creative work can make or deformation still within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of straight hole road magnetic material is it is characterised in that comprise the following steps:
(1) Nano silica sol is uniform with the aqueous solution of polyvinyl alcohol and sodium lauryl sulphate, described polyethylene is pure and strong
Spend for 2.5-5wt%, the concentration of sodium lauryl sulphate is 0.3-0.7g/ml, and thickness of silica gel is 38-45wt%, prepared nanometer
Ludox dispersion liquid；
(2) dispersion liquid that step (1) is obtained freezes as solid-state in liquid nitrogen；
(3) the solid dispersion liquid obtaining step (2) puts into the vacuum freeze drier that cryogenic temperature has reached -55--65 DEG C
In, open vacuum mode, vacuum freeze drier is in vacuum freezing mode 45-50h；
(4) sample preparing step (3) is placed in crucible, puts into calcining in resistance furnace, is warming up to 800- with 2-8 DEG C/min
900 DEG C, stop heating after insulation 0.5-1.5 hour, naturally cool to room temperature, obtain straight hole road silicon dioxide block；
(5) the silicon dioxide block preparing step (4) is immersed in the fecl3 solution of 0.5-2m, is 15pa bar in vacuum
Extracting vacuum under part, takes out sample after pressurize 20-40min, behind washes of absolute alcohol surface, is placed in baking oven, 80-110 DEG C
Under 1-1.5h is dried；
(6) concentration is the nabh4 of 0.1-0.2m or is reduced with the sample that h2 is obtained to step (5), obtains straight hole
Road magnetic coupling block materials.
2. preparation method as claimed in claim 1 is it is characterised in that reduced with h2 in described step 6), reduction temperature is
500-700 DEG C, it is incubated 2-4h.
3. preparation method as claimed in claim 1 is it is characterised in that use nabh4 reductase 12 0-40min in described step 6).
4. the straight hole road magnetic material obtained by any one of claim 1-3 preparation method.
5. application in liquid chromatograph, catalytic reaction and axonal reaction for the straight hole road magnetic material described in claim 4.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004189567A (en) * | 2002-12-13 | 2004-07-08 | Nippon Ceramic Co Ltd | Mn-zn ferrite |
| CN101797387B (en) * | 2009-12-14 | 2012-01-18 | 中南大学 | Magnetic targeting carrier capable of carrying gene and drug, preparation method and application thereof |
| CN102824931A (en) * | 2012-09-11 | 2012-12-19 | 复旦大学 | Three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and preparation method thereof |
| CN103146387A (en) * | 2013-03-19 | 2013-06-12 | 山东大学 | Process for preparing porous rare-earth luminescent material by freeze-drying method |
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2014
- 2014-04-11 CN CN201410146491.0A patent/CN104979061B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004189567A (en) * | 2002-12-13 | 2004-07-08 | Nippon Ceramic Co Ltd | Mn-zn ferrite |
| CN101797387B (en) * | 2009-12-14 | 2012-01-18 | 中南大学 | Magnetic targeting carrier capable of carrying gene and drug, preparation method and application thereof |
| CN102824931A (en) * | 2012-09-11 | 2012-12-19 | 复旦大学 | Three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and preparation method thereof |
| CN103146387A (en) * | 2013-03-19 | 2013-06-12 | 山东大学 | Process for preparing porous rare-earth luminescent material by freeze-drying method |
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