CN113463388B - Inorganic/high polymer composite film for preventive protection of paper cultural relics and preparation method thereof - Google Patents
Inorganic/high polymer composite film for preventive protection of paper cultural relics and preparation method thereof Download PDFInfo
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
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- D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention belongs to the field of polymer fibers, in particular to an inorganic/polymer composite film for preventive protection of paper cultural relics and a preparation method thereof, wherein a carbon source material is firstly dissolved in water and then subjected to hydrothermal reaction to obtain nano carbon spheres; uniformly mixing the synthesized nano carbon spheres with a titanium dioxide precursor, dissolving in a solvent, and performing hydrothermal reaction to obtain a composite nano material with a core-shell structure; then dissolving the high molecular polymer and the composite nano material in a solvent to form uniform high molecular solution for electrostatic spinning to obtain a composite fiber membrane; and then, dissolving an acrylic ester monomer and a light curing agent in water, spraying a curing solution on the composite fiber membrane, and finally, irradiating, curing and forming by using an ultraviolet lamp to obtain a final product. The composite fiber prepared by the invention can effectively achieve the performances of superhydrophobicity, ultraviolet shielding, antibiosis, bacteriostasis and the like under the condition of not changing the texture and pigment of paper cultural relics.
Description
Technical Field
The invention relates to the field of polymer fibers, in particular to an inorganic/polymer composite film for preventive protection of paper cultural relics and a preparation method thereof.
Background
The paper cultural relics are used as carriers for carrying histories and cultures, are important components of cultural heritage, contain a large number of precious cultural histories and records, and are one of the cultural relics which are difficult to store for a long time. Because the main raw materials of the paper cultural relics are plant fibers such as cellulose, and the oxygen bridge in the cellulose which connects glucose into long chains attracts H + Is a group which is easily oxidized (-CH) in the cellulose structure 2 OH and-OH) make it susceptible to a series of chemical reactions that initiate cleavage of the cellulose chain. Therefore, in the preservation process, the paper cultural relics are easily broken by the influence of environmental factors such as humidity, microorganisms, ultraviolet rays and the like, so that the mechanical strength is reduced, bacteria and pests are bred, and the paper cultural relics are damaged such as yellowing, brittle failure, breakage and the like, so that the preservation life, ornamental value and research value are greatly reduced.
Desirable properties of materials used to preserve paper products should include flexibility, transparency, cohesion, long term durability and reversibility, while the protection process should be fast, capable of wide use and not harmful to paper products. Some scientific studies on improving the strength of paper include wire mesh lamination, mylar encapsulation, radiation polymerization, parylene process and graft copolymer coating methods. However, all of these methods have some unavoidable drawbacks. The web itself is prone to aging, resulting in aging of the protected paper product, while the mylar film changes the appearance, optical properties, texture and thickness of the paper and hardens after the aging process. There is no certainty as to whether the radiation method has a positive or negative effect on paper remains. Parylene protection needs to be performed in vacuo, involving complex processes and stringent conditions. Direct resin coating also causes rapid aging of the paper due to the concentration difference between the surface and the interior of the paper, which is caused by poor wetting between the resin and the paper fibers. Graft polymerization can well protect cellulose-based substrates and introduce the advantages of graft polymers, such as resistance to biological attack. Consolidation is achieved by grafting processes that are difficult to separate. However, the difficulty of reversibility seems to be the biggest obstacle in application. Therefore, there is an urgent need for a paper preservation method that is efficient, convenient, harmless and stable for a long period of time.
In the aspect of paper cultural relics protection, researchers have developed composite fiber films for paper cultural relics protection, but at the same time, problems exist. For example, the patent (patent publication number CN 108425272B) entitled "a method for protecting paper documents by using electrostatic spinning fiber film" directly dopes ultraviolet screening agent and polymer to obtain composite fiber film for protecting paper cultural relics, only the composite fiber film with good hydrophobicity and ultraviolet screening effect is obtained, damage of fungus and bacteria to paper cultural relics is ignored, and damage of microorganisms to cultural relics cannot be slowed down. At present, composite fiber materials with super-hydrophobic property, high ultraviolet shielding property and high antibacterial activity can not be obtained through the combination of single nano particles and high polymers, and are used for the preventive protection of paper cultural relics. In addition, the functional nano particles are worn out and fall off in the use process through simple doping, so that the original excellent performance is lost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that: the preparation method of the inorganic/high polymer composite film for the preventive protection of the paper cultural relics has the advantages of simple material, multifunction collection, long-time use, simple and convenient operation, reasonable cost, large-scale preparation and safe use, and the inorganic/high polymer composite film for the preventive protection of the paper cultural relics and the preparation method thereof.
The invention also aims to provide the inorganic/high polymer composite film for preventive protection of paper cultural relics, which is prepared by the method. The inorganic ultraviolet screening agent/polymer composite film for preventive protection of paper cultural relics combines high-performance inorganic nano materials and polymer fiber films.
The aim of the invention is achieved by the following scheme:
the preparation method of the inorganic/high polymer composite film for preventive protection of paper cultural relics comprises the following steps:
s1, synthesizing a high-performance inorganic nano material: dissolving a carbon source material in water, and then performing hydrothermal reaction to obtain a nano carbon sphere; uniformly mixing the synthesized nano carbon spheres with a titanium dioxide precursor, dissolving in a solvent, and performing hydrothermal reaction to obtain a composite nano material with a core-shell structure;
s2, preparing a spinning solution and carrying out electrostatic spinning: dissolving a high molecular polymer and the composite nano material in a solvent to form a uniform high molecular solution; carrying out electrostatic spinning by taking the fiber as a spinning solution to obtain a composite fiber membrane;
s3, photo-curing treatment: and (3) dissolving the acrylic ester monomer and the photo-curing agent in water to prepare curing liquid, spraying the curing liquid on the composite fiber membrane, and finally, irradiating with an ultraviolet lamp for curing and forming to obtain a final product.
The carbon source material in the step S1 is preferably at least one of D-anhydrous glucose, L- (-) xylose, D- (+) -maltose monohydrate, fructose and sucrose, and the mass fraction of the carbon source material in water is 0.01% -20%;
the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃, and the time of the hydrothermal reaction is 3-12 h;
the precursor of the titanium dioxide in the step S1 is preferably at least one of tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, and the mass fraction of the precursor in the mixed solution is 0.5-15%;
the mass ratio of the nano carbon spheres to the titanium dioxide precursor in the step S1 is preferably 1:0.1-1.2.
The temperature of the hydrothermal reaction in the step S1 is 120-200 ℃ and the reaction time is 1-5 h.
The solvent in step S1 is preferably at least one of absolute ethanol, water, and absolute methanol.
The mass ratio of the composite nano material to the high molecular polymer in the step S2 is 0-0.8:1, and the dosage of the composite nano particles is not 0.
The high molecular polymer in step S2 is preferably at least one of polyvinylidene fluoride, polyacrylonitrile, hydrogenated poly (styrene-butadiene-styrene), polystyrene-polybutadiene-polystyrene block copolymer.
The solvent in the step S2 is at least one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and acetone.
The spinning parameters in the step S2 are that the spinneret is connected with 0.5-50 kV voltage (positive or negative), and the collecting device is connected with 0-50 kV voltage (positive or negative, opposite to the spinneret potential or grounded); the distance between the spinneret and the collecting device is 5-50 cm, and the supply speed of the spinning solution is 0.1-30 mL/h. The spinning environment temperature is 5-60 ℃ and the relative humidity is 25-95%.
The acrylic ester monomer in the step S3 is preferably at least one of pure acrylic ester, 1, 6-hexanediol diacrylate and pentaerythritol triacrylate, and the mass fraction of the acrylic ester monomer in the mixed solution is 0.5-15%;
the photocuring agent in the step S3 is preferably at least one of benzoin diethyl ether, dialkoxyacetophenone, chlorinated acetophenone and benzophenone;
the photo-curing time in the step S3 is preferably 0.01 to 1S; the mass ratio of the light curing agent to the acrylic ester monomer in the step S3 is preferably 0-0.8:1, and the dosage of the light curing agent is not 0.
The power of the ultraviolet lamp in the step S3 is preferably 24-60W.
An inorganic/high polymer composite film for preventive protection of paper cultural relics is prepared by the method. After the prepared fiber membrane is cut into a proper size, the paper cultural relics are wrapped, so that the multifunctional protection and durability effects are achieved.
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesis method of the nano particles provided by the invention has the advantages that raw materials are easy to obtain, and large-scale stable preparation can be performed. Meanwhile, by compounding with a carbon material, the absorption value of the nano particles in the visible light wave band is 20 times higher than that of the traditional titanium dioxide, the nano particles have good visible light shielding effect, the ultraviolet absorption performance of the nano particles is 10 times higher than that of the traditional titanium dioxide, and meanwhile, the nano particles bring extremely strong antibacterial performance.
2. The composite fiber prepared by the invention can effectively achieve the performances of superhydrophobicity, ultraviolet shielding, antibiosis, bacteriostasis and the like under the condition of not changing the texture and pigment of paper cultural relics. Meanwhile, the average diameter nano-scale and micro-scale fibers can be obtained by regulating and controlling spinning parameters and the types of high polymers.
3. The invention has simple process, reliable quality and high repeatability. The prepared composite fiber membrane can be used for preventive protection of paper cultural relics.
Drawings
Fig. 1 is a scanning electron micrograph of the nanocarbon ball prepared in example 1.
Fig. 2 is a scanning electron micrograph of the composite nanoparticle prepared in example 2.
Fig. 3 is a transmission electron micrograph of the composite nanoparticle prepared in example 2.
Fig. 4 is an ultraviolet-visible light absorption diagram of the composite nanoparticle prepared in example 3 and pure titanium dioxide.
FIG. 5 is a scanning electron microscope image of a composite fiber, wherein FIG. 5a is a scanning electron microscope photograph of a nanofiber prepared in example 4; fig. 5b is a scanning electron micrograph of the micro-sized fiber prepared in example 1.
FIG. 6 is a scanning electron microscope image of the composite fiber, wherein FIG. 6a is a scanning electron microscope photograph of the composite fiber prepared in example 1; fig. 6b is a scanning electron micrograph of the composite fiber prepared in example 2.
Fig. 7 is a graph of contact angle of the composite fiber prepared in example 3.
FIG. 8 is an antibacterial test chart of the composite fiber prepared in example 5.
Detailed Description
The present invention will be further described with reference to specific examples and drawings, but should not be construed as limiting the invention.
Example 1
Dissolving 0.5-g D-anhydrous glucose in 50mL of distilled water, adding the distilled water into a high-pressure hydrothermal reaction kettle, reacting for 10 hours at 180 ℃, and washing the mixture with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform morphology and size. Uniformly dispersing 0.5g of nano carbon spheres and 0.2g of butyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3 hours at 160 ℃, and washing the mixture with ethanol for multiple times to obtain the composite nano particles with the core-shell structure.
And dissolving polyvinylidene fluoride and the composite nano particles in a mixed solvent of N, N-dimethylformamide and acetone (the mass ratio is 4:1) to form a polymer solution with the mass fraction of 12wt%, wherein the mass ratio of the composite nano particles to the polymer is 0.8:1.
The spinneret is connected with +15kV voltage, and the receiving device is connected with-1 kV voltage. The distance between the spinneret and the receiving device was 15cm, and the spinning solution supply rate was 3mL/h. The spinning environment temperature is 25 ℃ and the relative humidity is 60%. And after spinning is finished, volatilizing the solvent completely to obtain a fiber final product.
Dissolving 10g of pure acrylic ester and 5g of benzoin diethyl ether in water to prepare a curing liquid, spraying the curing liquid on the composite fiber film, and finally, irradiating for 1s by using a 60W ultraviolet lamp to cure and shape to obtain a final product.
Example 2
Dissolving 0.25g D- (+) -maltose monohydrate in 50mL of distilled water, adding the distilled water into a high-pressure hydrothermal reaction kettle, reacting for 10 hours at 180 ℃, and washing the mixture with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform morphology and size. Uniformly dispersing 0.2g of nano carbon spheres and 0.2g of butyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3 hours at 160 ℃, and washing the mixture with ethanol for multiple times to obtain the composite nano particles with the core-shell structure.
And dissolving polyvinylidene fluoride and the composite nano particles in a mixed solvent of N, N-dimethylformamide and acetone (the mass ratio is 4:1) to form a polymer solution with the mass fraction of 12wt%, wherein the mass ratio of the composite nano particles to the polymer is 0.4:1.
The spinneret is connected with +13kV voltage, and the receiving device is connected with-3 kV voltage. The distance between the spinneret and the receiving device was 15cm, and the spinning solution supply rate was 2mL/h. The spinning environment temperature is 25 ℃ and the relative humidity is 60%. And after spinning is finished, volatilizing the solvent completely to obtain a fiber final product.
8g of 1, 6-hexanediol diacrylate and 2g of benzoin diethyl ether are dissolved in water to prepare a curing liquid, the curing liquid is sprayed on the composite fiber film, and finally, the composite fiber film is irradiated by a 30W ultraviolet lamp for 2s to be cured and molded to obtain a final product.
Example 3
Dissolving 0.1g of sucrose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 6 hours at 180 ℃, and washing the solution with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform shape and size. Uniformly dispersing 0.5g of nano carbon spheres and 0.2g of ethyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3 hours at 160 ℃, and washing the mixture with ethanol for multiple times to obtain the composite nano particles with the core-shell structure.
And dissolving the hydrogenated poly (styrene-butadiene-styrene) and the composite nano particles in a mixed solvent of tetrahydrofuran to form a polymer solution with the mass fraction of 14wt%, wherein the mass ratio of the composite nano particles to the polymer is 0.6:1.
The spinneret is connected with +14kV voltage, and the receiving device is connected with-2 kV voltage. The distance between the spinneret and the receiving device was 15cm, and the spinning solution supply rate was 1mL/h. The spinning environment temperature is 25 ℃ and the relative humidity is 60%. And after spinning is finished, volatilizing the solvent completely to obtain a fiber final product.
6g of pentaerythritol triacrylate and 6g of dialkoxyacetophenone are dissolved in water to prepare a curing liquid, the curing liquid is sprayed on the composite fiber membrane, and finally, a 40W ultraviolet lamp is used for irradiating for 1.5s to cure and form, so that a final product is obtained.
Example 4
Dissolving 0.15g L- (-) xylose in 50mL of distilled water, adding the distilled water into a high-pressure hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, and washing the mixture with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform shape and size. Uniformly dispersing 0.5g of nano carbon spheres and 0.4g of propyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3 hours at 160 ℃, and washing the mixture with ethanol for multiple times to obtain the composite nano particles with the core-shell structure.
And dissolving polyacrylonitrile and the composite nano particles in a mixed solvent of tetrahydrofuran to form a polymer solution with the mass fraction of 10wt%, wherein the mass ratio of the composite nano particles to the polymer is 1:1.
The spinneret is connected with +16kV voltage, and the receiving device is connected with-0.5 kV voltage. The distance between the spinneret and the receiving device was 15cm, and the spinning solution supply rate was 0.3mL/h. The spinning environment temperature is 25 ℃ and the relative humidity is 60%. And after spinning is finished, volatilizing the solvent completely to obtain a fiber final product.
10g of pentaerythritol triacrylate and 3g of chlorinated acetophenone are dissolved in water to prepare a curing liquid, the curing liquid is sprayed on the composite fiber membrane, and finally, a 40W ultraviolet lamp is used for irradiating for 1.5s to cure and form, so that a final product is obtained.
Example 5
Dissolving 0.05g of sucrose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 10 hours at 160 ℃, and washing the solution with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform shape and size. Uniformly dispersing 0.5g of nano carbon spheres and 0.6g of ethyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3 hours at 160 ℃, and washing the mixture with ethanol for multiple times to obtain the composite nano particles with the core-shell structure.
And dissolving polyacrylonitrile and the composite nano particles in a mixed solvent of dichloromethane to form a polymer solution with the mass fraction of 18wt%, wherein the mass ratio of the composite nano particles to polyvinylidene fluoride is 0.5:1.
The spinneret is connected with +18kV voltage, and the receiving device is connected with-1 kV voltage. The distance between the spinneret and the receiving device was 15cm, and the spinning solution supply rate was 0.5mL/h. The spinning environment temperature is 25 ℃ and the relative humidity is 60%. And after spinning is finished, volatilizing the solvent completely to obtain a fiber final product.
Dissolving 10g of pure acrylic ester and 8g of benzophenone in water to prepare a curing liquid, spraying the curing liquid on the composite fiber film, and finally, irradiating for 1s by using a 60W ultraviolet lamp to cure and shape to obtain a final product.
Fig. 1 is a scanning electron micrograph of a nanocarbon sphere prepared by the technical method provided by the present invention, and the average diameter of nanoparticles is about 300nm. Fig. 2 is a scanning electron micrograph of composite nanoparticles prepared by the technical method provided by the present invention, with an average diameter of about 320nm. Fig. 3 is a transmission electron micrograph of composite nanoparticles prepared by the technical method provided by the present invention, with an average diameter of about 320nm.
Fig. 5 is a scanning electron micrograph of a fibrous membrane prepared by the technical method provided by the present invention. The average diameter nano-scale and micro-scale fiber can be obtained by regulating and controlling the spinning parameters and the types of high polymers.
Fig. 4 is an ultraviolet-visible light absorption diagram of the composite nanoparticle prepared by the technical method provided by the invention and pure titanium dioxide. The test shows that the composite nano particle has high absorption value in ultraviolet and visible light bands, and the titanium dioxide has high absorption peak only in ultraviolet band.
Fig. 6 is a scanning electron micrograph of 2 composite fibers prepared by the technical method provided by the present invention (a graph obtained by example 1 and b graph obtained by example 2).
FIG. 7 is a photograph showing the contact angle of the composite fiber prepared by the technical method disclosed by the invention, which exceeds 150 degrees, and basically has super-hydrophobic performance.
Fig. 8 is a photograph of a composite fiber bacteriostasis prepared by the technical method disclosed by the invention, which shows obvious bacteriostasis zones and has certain bacteriostasis performance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the inorganic/high polymer composite film for preventive protection of paper cultural relics is characterized by comprising the following steps:
s1, synthesizing a high-performance inorganic nano material: dissolving a carbon source material in water, and then performing hydrothermal reaction to obtain a nano carbon sphere; uniformly mixing the synthesized nano carbon spheres with a titanium dioxide precursor, dissolving in a solvent, and performing hydrothermal reaction to obtain a composite nano material with a core-shell structure;
s2, preparing a spinning solution and carrying out electrostatic spinning: dissolving a high molecular polymer and the composite nano material in a solvent to form a uniform high molecular solution; carrying out electrostatic spinning by taking the fiber as a spinning solution to obtain a composite fiber membrane;
s3, photo-curing treatment: dissolving an acrylic ester monomer and a photo-curing agent in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally, irradiating with an ultraviolet lamp for curing and forming to obtain a final product;
the mass ratio of the nano carbon spheres to the titanium dioxide precursor in the step S1 is 1:0.1-1.2.
2. The method according to claim 1, characterized in that: the carbon source material in the step S1 is at least one of D-anhydrous glucose, L- (-) -xylose, D- (+) -maltose monohydrate, fructose and sucrose; the mass fraction of the carbon source material in water is 0.01% -20%.
3. The method according to claim 1, characterized in that: the precursor of the titanium dioxide in the step S1 is at least one of tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate; the mass fraction of the water in the mixed solution is 0.5-15%.
4. The method according to claim 1, characterized in that: the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃, and the time of the hydrothermal reaction is 3-12 h; the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃ and the reaction time is 1-5 h.
5. The method according to claim 1, characterized in that: the acrylic ester monomer in the step S3 is at least one of pure acrylic ester, 1, 6-hexanediol diacrylate and pentaerythritol triacrylate; the mass fraction of the water in the mixed solution is 0.5-15%.
6. The method according to claim 1, characterized in that: the solvent in the step S2 is at least one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and acetone; the photocuring agent in the step S3 is at least one of benzoin diethyl ether, dialkoxy acetophenone, chlorinated acetophenone and benzophenone.
7. The method according to claim 1, characterized in that: in the step S3, the mass ratio of the light curing agent to the acrylic ester monomer is 0-0.8:1, and the dosage of the light curing agent is not 0.
8. The method according to claim 1, characterized in that: the spinning parameters in the step S2 are that the spinneret is connected with 0.5-50 kV voltage, and the collecting device is connected with 0-50 kV voltage; the distance between the spinneret and the collecting device is 5-50 cm, and the supply speed of the spinning solution is 0.1-30 mL/h; the spinning environment temperature is 5-60 ℃ and the relative humidity is 25-95%; and in the step S3, the power of the ultraviolet lamp is 24-60W.
9. An inorganic/polymeric composite film for the prophylactic protection of paper relics prepared according to the method of any one of claims 1 to 8.
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| CN102225330A (en) * | 2011-04-20 | 2011-10-26 | 东南大学 | Method for preparing photochemical catalyst/graphene one-dimensional nuclear shell compound structure by using photochemical catalysis method |
| CN106111211A (en) * | 2016-06-25 | 2016-11-16 | 董晓 | A kind of modified core shell structure Fe3o4/ C/TiO2the preparation method of composite |
| CN106167551A (en) * | 2016-08-04 | 2016-11-30 | 华南理工大学 | A kind of water resistant washes away super-hydrophobic composite film and preparation method thereof and application |
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| CN101229957B (en) * | 2007-12-25 | 2010-11-17 | 山东大学 | SiO2/TiO2 hollow compound structural material as well as preparation method and uses thereof |
| WO2012051641A1 (en) * | 2010-10-22 | 2012-04-26 | University Of Queensland | Metal oxide particles |
| CN101979449B (en) * | 2010-11-30 | 2013-04-24 | 中国乐凯胶片集团公司 | Ultraviolet curing coating for white board |
| CN108425272B (en) * | 2018-02-26 | 2021-03-23 | 嘉兴学院 | Method for protecting paper document by adopting electrostatic spinning fiber membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225330A (en) * | 2011-04-20 | 2011-10-26 | 东南大学 | Method for preparing photochemical catalyst/graphene one-dimensional nuclear shell compound structure by using photochemical catalysis method |
| CN106111211A (en) * | 2016-06-25 | 2016-11-16 | 董晓 | A kind of modified core shell structure Fe3o4/ C/TiO2the preparation method of composite |
| CN106167551A (en) * | 2016-08-04 | 2016-11-30 | 华南理工大学 | A kind of water resistant washes away super-hydrophobic composite film and preparation method thereof and application |
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