CN108993426A - A kind of Magnetic Cellulose Particles and preparation method thereof - Google Patents
A kind of Magnetic Cellulose Particles and preparation method thereof Download PDFInfo
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- CN108993426A CN108993426A CN201810831017.XA CN201810831017A CN108993426A CN 108993426 A CN108993426 A CN 108993426A CN 201810831017 A CN201810831017 A CN 201810831017A CN 108993426 A CN108993426 A CN 108993426A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to a kind of Magnetic Cellulose Particles and preparation method thereof, belong to filtering material field, are made of nano ferriferrous oxide granule, cellulose and functional group；The cellulose dopen Nano ferriferrous oxide particles and be in bulk；The functional group adheres on cellulose, including carbonyl, amino, carboxyl or/and sulfonic group.The present invention uses the absorbability particle of nanometer, the filtering of heavy metal or dyestuff is carried out using suction type, this filter type compared to the heavy metals processing method such as above-mentioned chemical precipitation method, ion-exchange, electrolysis method, have many advantages, such as it is at low cost, easy to operate, do not generate secondary pollution, adsorbent material regenerating easily.
Description
Technical field
The present invention relates to a kind of Magnetic Cellulose Particles and preparation method thereof, belong to absorption or filtering material field.
Background technique
According to the report of the World Health Organization, the disease of the mankind 80% is due to having drunk contaminated water, with the world
Population and industrialization degree increase sharply, and water pollution especially heavy metal ion increasingly sharpens to the pollution of water environment bring.It dislikes
The water contamination accident of property frequently occurs, and heavy metal water pollution has become global problem of environmental pollution.Animals and humans exist
Drink containing the exceeded sewage of heavy metal ion or it is edible containing the exceeded crops of heavy metal ion after, due to enrichment its
Harm is amplified, and is not easy to be metabolized by organism.Due to the very strong toxicity of heavy metal ion, duration and not biodegradable
Property, include poisoning, nervous system injury to the harm of human body and lead to cancer etc., seriously threatens the health of animals and humans,
The problem of pollution, also increasingly becomes the environmental problem to become increasingly conspicuous.The minimizing technology of Heavy Metals in Waters ion has very much
Research report, including classical chemical precipitation method, ion-exchange, electrolysis method, film filtering and oxidation-reduction method etc., these sides
Method has that investment is big, operating cost is high, operational administrative trouble, some the problem of even there are also secondary pollutions.
Summary of the invention
It is an object of the present invention to solve the above problems, devises raw materials of the present invention and be easy to get, be cheap, is green
Colour circle is protected, and composite magnetic particle preparation process is simple, design is reasonable and easy to operate, easy to accomplish and industrialization, and to a huge sum of money
Belong to and the adsorption effect of waste water from dyestuff is good, and repeatable, circulation is used for multiple times.
The technical solution adopted by the present invention to solve the technical problems is:
The present invention discloses a kind of Magnetic Cellulose Particles, by nano ferriferrous oxide granule, cellulose and functional group group
At；The cellulose dopen Nano ferriferrous oxide particles and be in bulk；The functional group adheres on cellulose, including carbonyl
Base, amino, carboxyl or/and sulfonic group.
It using modified cellulose is tested, is wrapped in outside magnetic particle, the composite fibre biscuit porcelain of core-shell structure is made
Property granule adsorbent.So that the adsorbent had not only had the performance of magnetic material, but also have the function of modified cellulose, it can be by it
It applies in terms of other function material, and stepping up with scientific research technology, the magnetic composite containing special groups
Can with electric field in environment, magnetic field variation and change, especially have paramagnetic particle can be under the action of external magnetic field
Magnetic is magnetized and put to moment, and it is more wide that this has obtained it in terms of purification of water quality, wastewater treatment, target administration, cell
General application.
Further, the magnetic fluid containing nano ferriferrous oxide granule the preparation method is as follows: according to iron ion and it is ferrous from
Sub- molar ratio is that the amount of 1-1.5 weighs Iron(III) chloride hexahydrate and Iron dichloride tetrahydrate respectively, is dissolved in water, adjusts solution
PH >=10 are heated to 70 DEG C -85 DEG C under anti-oxidation environment later and stir to after chemically reacting completely, carry out Magneto separate simultaneously
Clear liquid is removed, then several times with deionized water and washes of absolute alcohol, obtained solid is obtained by ethyl alcohol constant volume and ultrasound 30min
Magnetic fluid containing ferriferrous oxide particles.
The magnetic fluid containing nanometer containing ferriferrous oxide particles can be obtained by this method, partial size can reach nanometer
Grade, to be conducive to the preparation of this equipment cellulose grain, and improves its filter effect, while improving the strong of its saturated magnetization
Degree.
Further, for the cellulose using the cellulose for being modified tealeaf residue, preparation method is as follows: tealeaf residue is successively washed
Impurity elimination, drying, smashing, sieving are washed, tea powder is obtained；It mixes the citric acid solution and tea powder that concentration is 5%-10% and filters, it will
Drying obtains powdered cellulose after the tea powder particle filtered out cleans repeatedly repeatedly.Cellulose used in the present invention has
The features such as biodegradability, environment compatibility.Using tealeaves as cellulose origin, it is not only rich in fiber, is contained simultaneously
Tealeaf residue, is then modified by tea polyphenols, theanine isoreactivity substance, solves general fibre element to the adsorption efficiency of adsorbent
It is not high, be not easy to adsorbate separation, the disadvantages of renewable performance is poor, make in cellulose surface by being crosslinked, being copolymerized, be modified etc. just
Method introduces such as-CO ,-NH2 ,-COOH ,-SO3H multiple functions group on material, improves adsorption effect, reduces costs.
A kind of preparation method of Magnetic Cellulose Particles of the invention, the following steps are included:
Step 1: after the monomer with functional group is dissolved in water, adding crosslinking agent and stir evenly, it is mixed that crosslinking is made
The mass ratio of conjunction liquid, monomer and crosslinking agent is 1-1.5；
Step 2: in 50 DEG C of waters bath with thermostatic control, by cellulose plus ultrapure water and after mixing evenly；Gelatinization；After cooling, it is added
The mass ratio of sodium hydroxide and urea, sodium hydroxide and urea is 2-2.5, and 3h is then dispersed with stirring under condition of ice bath, ultrasound
30min；After the magnetic fluid of initiator and nano ferriferrous oxide is successively added again, ultrasonic disperse 30min is obtained containing magnetic four
Fe 3 O mixed liquor；
Step 3: by warming-in-water to 75 DEG C, mixed liquor will be crosslinked and be added containing magnetic ferroso-ferric oxide mixed liquor, through handing over
Connection and copolyreaction are made Magnetic Cellulose Particles and Magnetic Cellulose Particles are washed to neutrality using magnetic separation technique, use
Dehydrated alcohol is dried after washing；
The functional group includes carbonyl, amino, carboxyl or/and sulfonic group.
The Magnetic Cellulose Particles that above step prepares, due to obtaining magnetic cellulose using chemistry and coprecipitation
Particle, the ferroso-ferric oxide as carrier can finally obtain the cellulose particles that partial size is about 195nm at the state of magnetic fluid
Grain, and saturation magnetization is that can reach 31emu/g.And by introducing carbonyl, amino, carboxyl or/and sulfonic group, from
And improve the adsorption effect of the ingredients such as heavy metal or dyestuff.
Further, the monomer includes acrylamide, acrylic acid, methacrylaldehyde or/and methyl methacrylate.
Further, the crosslinking agent includes N, N'- methylene-bisacrylamide, glutaraldehyde or/and epichlorohydrin.
Further, the initiator includes initiator, such as ammonium ceric nitrate, ammonium persulfate and sodium sulfite mixture or/and
Sodium bisulfate and potassium peroxydisulfate mixture.
Further, cellulose the preparation method is as follows: take the tealeaves or discarded tealeaf residue through repeatedly being impregnated, spend
Ion water washing removes impurity, dries at 100 DEG C, takes fine grain tea powder using the sieve sieve of 100 mesh after smashing；It prepares
5-12g tea powder is added in the citric acid solution that 50mL mass percent is 10%, mixes, is stirred to react 2-4h, filters, by product
12h is dried in 60 DEG C of baking ovens after being cleaned repeatedly with deionized water.
Further, the preparation method of magnetic fluid: distinguish according to iron ion and ferrous ion molar ratio for the amount of 1:(1-1.5)
Iron(III) chloride hexahydrate and Iron dichloride tetrahydrate are weighed, is dissolved in water, pH value of solution=10 are adjusted, is added in a nitrogen environment later
Heat is to 70 DEG C -85 DEG C, and after 1000r/min stirring 2-3h makes chemical reaction completely, solution stand magnetic field nearby carries out Magneto separate, to
Solution is clarified completely, removes last time clear liquid, and then several times with deionized water and washes of absolute alcohol, obtained solid is scattered in
In 250mL volumetric flask, ethyl alcohol constant volume, ultrasonic 30min obtains the magnetic fluid of nano ferriferrous oxide.
The invention has the benefit that
1, raw materials of the invention are easy to get, are cheap, is environmentally protective, composite magnetic microspheres are simple,
It is reasonable and easy to operate to design, easy to accomplish and industrialization, and good to the adsorption effect of heavy metal and waste water from dyestuff；
2, the present invention uses the absorbability particle of nanometer, and the filtering of heavy metal or dyestuff is carried out using suction type, this
Filter type has at low cost, behaviour compared to the heavy metals processing method such as above-mentioned chemical precipitation method, ion-exchange, electrolysis method
Work is simple, does not generate the advantages that secondary pollution, adsorbent material regenerating easily；
3, the present invention uses organic matter adsorbent, and source is wider, and its is cheap and easy to get, adsorption effect is good, can resource
Significant advantages and the favor by environmentalists such as change, is widely used in the removal of Heavy Metals in Waters.
Detailed description of the invention
Fig. 1 is the topology example figure of Magnetic Cellulose Particles；
Fig. 2 is powder diagram of the Magnetic Cellulose Particles under X-ray；
Fig. 3 is spectrogram of the Magnetic Cellulose Particles under infrared light；
Fig. 4 is the intensity of magnetization comparison diagram of Magnetic Cellulose Particles and ferroso-ferric oxide.
Appended drawing reference: 1- cellulose, 2- ferriferrous oxide particles, 3- functional group.
Specific embodiment
Embodiment 1
As shown in Figure 1, a kind of Magnetic Cellulose Particles of the invention, by nano ferriferrous oxide granule, cellulose and function
It can group composition.
Cellulose and nano ferriferrous oxide granule adulterate together, and bulk structure is collectively formed, and cellulose, which uses, to be changed
The cellulose of property tealeaf residue.
Functional group adheres on cellulose, including carbonyl, amino, carboxyl or/and sulfonic group.
Embodiment 2
The preparation method of Magnetic Cellulose Particles in embodiment 1, comprising the following steps:
Step 1: after the monomer with functional group is dissolved in water, adding crosslinking agent and stir evenly, it is mixed that crosslinking is made
The mass ratio of conjunction liquid, monomer and crosslinking agent is 1-1.5；
Step 2: in 50 DEG C of waters bath with thermostatic control, by cellulose plus ultrapure water and after mixing evenly；Gelatinization；After cooling, it is added
The mass ratio of sodium hydroxide and urea, sodium hydroxide and urea is 2-2.5, and 3h is then dispersed with stirring under condition of ice bath, ultrasound
30min；After the magnetic fluid of initiator and nano ferriferrous oxide is successively added again, ultrasonic disperse 30min is obtained containing magnetic four
Fe 3 O mixed liquor；
Step 3: by warming-in-water to 75 DEG C, mixed liquor will be crosslinked and be added containing magnetic ferroso-ferric oxide mixed liquor, through handing over
Connection and copolyreaction are made Magnetic Cellulose Particles and Magnetic Cellulose Particles are washed to neutrality using magnetic separation technique, use
Dehydrated alcohol is dried after washing.
The monomer includes acrylamide, acrylic acid, methacrylaldehyde or/and methyl methacrylate.
The crosslinking agent includes N, N'- methylene-bisacrylamide, glutaraldehyde or/and epichlorohydrin.
The initiator includes initiator, such as ammonium ceric nitrate, ammonium persulfate and sodium sulfite mixture or/and sodium bisulfate
With potassium peroxydisulfate mixture.
Embodiment 3
In the present invention, embodiment 1 or the cellulose in embodiment 2 are repeatedly impregnated the preparation method is as follows: taking
Tealeaves or discarded tealeaf residue, removal impurity is washed with deionized, is dried at 100 DEG C, after smashing use 100 mesh sieve
Sieve takes fine grain tea powder；The citric acid solution that 50mL mass percent is 10% is prepared, 5-12g tea powder is added, mixes, stirring
2-4h is reacted, filtering dries 12h in 60 DEG C of baking ovens after cleaning product repeatedly with deionized water.
Embodiment 4
In the present invention, the preparation method of the magnetic fluid containing the ferriferrous oxide particles in embodiment 1 or embodiment 2: press
According to iron ion and ferrous ion molar ratio weighs Iron(III) chloride hexahydrate respectively for the amount of 1:(1-1.5) and four chloride hydrates are sub-
Iron is dissolved in water, and adjusts pH value of solution=10, is heated to 70 DEG C -85 DEG C in a nitrogen environment later, 1000r/min stirs 2-3h
After making chemical reaction completely, solution stand magnetic field nearby carries out Magneto separate, clarifies completely to solution, removes last time clear liquid, then
Several times with deionized water and washes of absolute alcohol, obtained solid is scattered in 250mL volumetric flask, ethyl alcohol constant volume, ultrasonic 30min,
Obtain the magnetic fluid of nano ferriferrous oxide.
Embodiment 5
In the present invention, using the Magnetic Cellulose Particles carry out copper ion adsorption experiment steps are as follows: take a certain amount of
Magnetic Cellulose Particles are added water and form adsorbent, and adsorbent is added to the copper-bath that 20mL initial concentration is 80mg/L
In, pH=5 value is adjusted, vibrates 3h at room temperature, is taken out, carries out Magneto separate using external magnetic field, it is anti-with atom spectrophotometric determination
Answer the content of front and back copper ion.Prepared by the method tea grounds composite magnetic microballoon carries out adsorption treatment, copper ion in solution
Maximal absorptive capacity be 21.2mg/g, removal rate can achieve 91% or more.
The present invention is wrapped in outside magnetic particle using modified cellulose is tested, and the compound fibre of core-shell structure is made
Tie up biscuit porcelain microsphere adsorbing agent.So that the adsorbent had not only had the performance of magnetic material, but also have the function of modified cellulose, it can
To be applied in terms of other function material, and stepping up with scientific research technology, the magnetism containing special groups are multiple
Condensation material can with electric field in environment, magnetic field variation and change, especially have paramagnetic microballoon can be in external magnetic field
Acting on lower moment magnetizes and puts magnetic, this obtains it in terms of purification of water quality, wastewater treatment, target administration, cell
More it is widely applied.Simultaneously as cellulose is a kind of natural polymers important, growth is more stable, tool
There is the features such as biodegradability, environment compatibility.And fiber is not only rich in tealeaf residue, also containing tea polyphenols, theanine etc.
Active material tests cellulose used to the modified preparation of tealeaf residue, can be improved adsorption effect, general fibre element can be overcome to inhale
The disadvantages of attached dose of adsorption efficiency is not high, is not easy to adsorbate separates, renewable performance is poor.In addition, passing through in cellulose surface
The methods of crosslinking, copolymerization, modified, introduce such as-CO ,-NH2 ,-COOH ,-SO3H multiple functions group, further on material
Adsorption effect is improved, while tealeaf residue has been subjected to waste utilization again, is reduced costs.
Abscissa in Fig. 2 are as follows: angle of diffraction, unit are as follows: °；Ordinate are as follows: diffracted intensity, the figure shows: this product is in phase
The angle of diffraction answered all has diffraction maximum, illustrates that this product has wrapped up Fe3O4 magnetic nano-particle really；
Abscissa in Fig. 3 are as follows: wavelength, unit are as follows: nm；Ordinate are as follows: transmitance, unit are as follows: %, the figure shows: this production
Product have ferroferric oxide magnetic nano-particles, while having the functional groups such as carbonyl, amino and carboxyl；
Abscissa in Fig. 4 are as follows: magnetic field strength, unit are as follows: Oe；Ordinate are as follows: the intensity of magnetization, unit are as follows: emu/g, the figure
Indicate: this product saturation magnetic field intensity with higher can be attracted simultaneously quick separating under the action of external magnetic field；T- in figure
MCMs is the abbreviation of Magnetic Cellulose Particles.
Above-described embodiment does not limit the embodiments just for the sake of clearly illustrating done citing.For
For those skilled in the art, other different forms of changes or modifications may be made based on the above description.
There is no necessity and possibility to exhaust all the enbodiments.And obvious changes or variations extended from this are still
In protection scope of the present invention.
Claims (9)
1. a kind of Magnetic Cellulose Particles, which is characterized in that by nano ferriferrous oxide granule, cellulose and functional group group
At；The cellulose dopen Nano ferriferrous oxide particles and be in bulk；The functional group adheres on cellulose, including carbonyl
Base, amino, carboxyl or/and sulfonic group.
2. Magnetic Cellulose Particles as described in claim 1, which is characterized in that magnetic current of its nanometer containing ferriferrous oxide particles
Body the preparation method is as follows: being 1:(1-1.5 according to iron ion and ferrous ion molar ratio) amount weigh six hydration trichlorines respectively
Change iron and Iron dichloride tetrahydrate, is dissolved in water, adjusts pH >=10 of solution, be heated to 70 under anti-oxidation environment later
It DEG C -85 DEG C and stirs to after chemically reacting completely, carries out Magneto separate and simultaneously remove clear liquid, it is then clear with deionized water and dehydrated alcohol
It washes several times, obtained solid obtains the magnetic fluid containing ferriferrous oxide particles by ethyl alcohol constant volume and ultrasound 30min.
3. Magnetic Cellulose Particles as described in claim 1, which is characterized in that the cellulose is using the fibre for being modified tealeaf residue
Dimension element, preparation method are as follows: tealeaf residue successively being washed to impurity elimination, drying, smashing, sieving, obtains tea powder；Mixing concentration is
The citric acid solution and tea powder of 5%-10% simultaneously filter, and drying obtains powder after the tea powder particle that will filter out cleans repeatedly repeatedly
The cellulose of shape.
4. a kind of preparation method of Magnetic Cellulose Particles, which comprises the following steps:
Step 1: it after the monomer with functional group is dissolved in water, adds crosslinking agent and stirs evenly, crosslinking mixed liquor is made,
The mass ratio of monomer and crosslinking agent is 1-1.5；
Step 2: in 50 DEG C of waters bath with thermostatic control, by cellulose plus ultrapure water and after mixing evenly；Gelatinization；After cooling, hydrogen-oxygen is added
The mass ratio of change sodium and urea, sodium hydroxide and urea is 2-2.5, and 3h is then dispersed with stirring under condition of ice bath, ultrasound
30min；After the magnetic fluid of initiator and nano ferriferrous oxide is successively added again, ultrasonic disperse 30min is obtained containing magnetic four
Fe 3 O mixed liquor；
Step 3: by warming-in-water to 75 DEG C, mixed liquor will be crosslinked and be added containing magnetic ferroso-ferric oxide mixed liquor, it is crosslinked and
Magnetic Cellulose Particles are made in copolyreaction, using magnetic separation technique, Magnetic Cellulose Particles are washed to neutrality, use is anhydrous
Ethyl alcohol is dried after washing；
The functional group includes carbonyl, amino, carboxyl or/and sulfonic group.
5. the preparation method of Magnetic Cellulose Particles as claimed in claim 4, which is characterized in that the monomer includes acryloyl
Amine, acrylic acid, methacrylaldehyde or/and methyl methacrylate.
6. the preparation method of Magnetic Cellulose Particles as claimed in claim 4, which is characterized in that the crosslinking agent includes N,
N'- methylene-bisacrylamide, glutaraldehyde or/and epichlorohydrin.
7. the preparation method of Magnetic Cellulose Particles as claimed in claim 4, which is characterized in that the initiator includes causing
Agent, such as ammonium ceric nitrate, ammonium persulfate and sodium sulfite mixture or/and sodium bisulfate and potassium peroxydisulfate mixture.
8. the preparation method of Magnetic Cellulose Particles as claimed in claim 4, which is characterized in that the preparation method of cellulose is such as
Under: tealeaves or discarded tealeaf residue through repeatedly being impregnated are taken, removal impurity is washed with deionized, is dried at 100 DEG C,
Fine grain tea powder is taken using the sieve sieve of 100 mesh after smashing；The citric acid solution that 50mL mass percent is 10% is prepared, is added
Enter 5-12g tea powder, mix, be stirred to react 2-4h, filter, is dried in 60 DEG C of baking ovens after product is cleaned repeatedly with deionized water
12h。
9. the preparation method of Magnetic Cellulose Particles as claimed in claim 4, which is characterized in that the preparation method of magnetic fluid:
Iron(III) chloride hexahydrate is weighed respectively for the amount of 1:(1-1.5) according to iron ion and ferrous ion molar ratio and four chloride hydrates are sub-
Iron is dissolved in water, and adjusts pH value of solution=10, is heated to 70 DEG C -85 DEG C in a nitrogen environment later, 1000r/min stirs 2-3h
After making chemical reaction completely, solution stand magnetic field nearby carries out Magneto separate, clarifies completely to solution, removes last time clear liquid, then
Several times with deionized water and washes of absolute alcohol, obtained solid is scattered in 250mL volumetric flask, ethyl alcohol constant volume, ultrasonic 30min,
Obtain the magnetic fluid of nano ferriferrous oxide.
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Cited By (7)
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| CN110681361A (en) * | 2019-09-21 | 2020-01-14 | 天津大学 | Preparation method and application of magnetic cellulose microspheres with core-shell structure |
| CN111514863A (en) * | 2020-04-28 | 2020-08-11 | 合肥工业大学 | Heavy metal composite adsorption material prepared by taking banana peel as raw material and preparation method thereof |
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| CN113817179A (en) * | 2021-07-27 | 2021-12-21 | 南京林业大学 | Preparation method of nanofiber magnetofluid, nanofiber magnetofluid and application |
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| CN115075055B (en) * | 2022-06-15 | 2023-04-18 | 石家庄铁道大学 | Nano magnetic oxide composite tea paper and preparation method thereof |
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