CN103755984A - Method for preparing macromolecular nano composite membrane enriching inorganic filler on surface - Google Patents
Method for preparing macromolecular nano composite membrane enriching inorganic filler on surface Download PDFInfo
- Publication number
- CN103755984A CN103755984A CN201310750872.5A CN201310750872A CN103755984A CN 103755984 A CN103755984 A CN 103755984A CN 201310750872 A CN201310750872 A CN 201310750872A CN 103755984 A CN103755984 A CN 103755984A
- Authority
- CN
- China
- Prior art keywords
- film forming
- mineral filler
- composite membrane
- high molecular
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing a macromolecular nano composite membrane enriching inorganic filler on the surface, which is characterized by specifically comprising the following steps: (1) dissolving macromolecules and inorganic filler forming a membrane through phase inversion into a solvent to obtain mother liquid; (2) placing the mother liquid on a conductive membrane forming panel; (3) applying an electrostatic field vertical to the conductive membrane forming panel to the conductive membrane forming panel, wherein the electrostatic field promotes phase inversion of the mother liquid to obtain the macromolecular nano composite membrane enriching inorganic filler on the surface. After the inorganic filler is enriched on the surface, more properties of the macromolecular material can be obtained, and the method is particularly suitable for preparing materials with surface wear resistance, acid-alkali resistance, fire resistance, luminescence and the like.
Description
Technical field
The preparation method who the present invention relates to a kind of surface abrasion resistance, acid and alkali-resistance, the material such as fire-resistant, luminous, relates in particular to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler.
Background technology
Material surface structure design and performance regulation and control are study hotspot and the difficult point of macromolecular material high performance always.At polymer surface, form inorganic layer, can make material surface present the characteristic of inorganic materials, make up the deficiency in polymer-material wear-resistant damage property, erosion resistance and thermotolerance, in addition, can also give polymer surface some special performance, as photocatalytic and electroconductibility etc.Patent US8012578 has announced a kind of thermal plastic high polymer and compound method of metal oxide prepared.By controlling the sedimentation rate of thermal plastic high polymer and metal oxide, obtain the nano composite membrane of macromolecule surface enriched in oxygen SiClx.Patent CN 100396825C has announced a kind of preparation method of metal-base nano-composite cladding material.The nano-carbon tube-nano tungston carbide composite powder preparing is utilized to plasma modification, it is scattered in the electroplate liquid containing nickel ion, cupric ion or cobalt ion, under electric field driven, CNT (carbon nano-tube)-nanometer tungsten carbide and nickel, cupric ion or cobalt ion move simultaneously, in metal material surface deposition, form metal-based nano carbon pipe-nanometer tungsten carbide composite deposite.(the Chemistry of Materials such as Fong, 2001,13,4123-4129) adopt the surface of oxygen plasma treatment polycaprolactam (PA6)/polynite (MMT) nano composite material, the high-energy etching of plasma generation surperficial polymer segment, finally on surface, forming thickness is the inertia MMT layer of 1-4 nm, makes composite material surface present significant passivity and self-healing.Yet, the MMT lamellar orientation being scattered in before processing in PA6 matrix differs, and causes surface height after processing to rise and fall indefinite, and the MMT layer thickness of formation is uneven, it is various to be orientated, the final surfaceness forming is high, and cannot reach the perfect condition being covered by compact inorganic packing layer completely.Therefore, the surface properties such as barrier, abrasion resistance and oilness all has certain loss.
Additive used in Process Technology of Polymer, is adding man-hour or under specific ambiance, can be in material surface generation enrichment, and surface segregation phenomenon that Here it is (Segregation).From thermodynamic (al) angle, according to Gibbs adsorption isotherm, in multicomponent mixture, for reducing surface free energy, the component of low surface energy is always tended to, to surface transport (Migration), finally cause material surface to occur segregation phenomenon.The wet-formed process of phase inversion process is the process that high polymeric solution is separated in precipitation bath.First, polymkeric substance is dissolved in solvent to preparation film forming mother liquor.Further, make solvent evaporates, mother liquor system is separated, obtain polymeric membrane.Yet, not yet find that at present a step is prepared the method for surface enrichment mineral filler in phase inversion process wet method film-forming process.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler, the present invention applies electrostatic field on the basis of phase inversion process wet method film forming, the orientation movement of strengthening mineral filler in material filming process, in composite material shaping process, make part mineral filler uniform fold in polymer-based surface, obtain the organic/inorganic composite film of surperficial high performance.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler, concrete preparation process is as follows: (1) can be dissolved in solvent by polymer and the mineral filler of phase inversion process wet method film forming, prepares mother liquor; (2) mother liquor is placed on conduction film forming flat board; (3) on conduction film forming flat board, apply the electrostatic field perpendicular to conduction film forming flat board, this electrostatic field impels mother liquor inversion of phases, obtains the high molecular nanometer composite membrane of surface enrichment mineral filler.
Described polymer is nylon, polystyrene or polyvinyl alcohol, and wherein polymer is preferably nylon.
Described solvent is trifluoroethanol, methyl alcohol, tetrahydrofuran (THF), dehydrated alcohol or deionized water, and wherein solvent is preferably trifluoroethanol or formic acid.
Described mineral filler is polysilsesquioxane, clay, silicon-dioxide, Graphene, metal oxide or rare-earth fluorescent filler.
Described electrostatic field applies formation by direct supply, and the voltage of described direct supply is 0V-10000V, and wherein preferred voltage is 100V-1000V.
Polymer in described mother liquor and the mass ratio of solvent are 0.001g/ml-10g/ml, and preferred mass is than being 0.01g/ml-1g/ml.
Mineral filler in described mother liquor and high molecular mass ratio are 0.01%-50%, and preferred mass is than being 0.1%-20%, and more preferably mass ratio is 1%-10%.
Described metal oxide is Fe
3o
4or CuO.
Described rare-earth fluorescent filler is NaYF
4or NaYbF
4.
The top of conduction film forming flat board is provided with conduction film forming upper plate, the dull and stereotyped ground connection of described conduction film forming, and described conduction film forming upper plate connects power supply.
Key of the present invention is to select suitable strength of electric field, solves the resistance in mineral filler transition process, as the interaction of polymer and mineral filler, high molecular crystallization behavior.
Sample structure analysis of the present invention: adopt the surface characteristic element of energy spectrum analysis instrument analytic sample in scanning electron microscope to distribute as Si, Na element etc.; Adopt Static Contact horn cupping to measure composite film material surface hydrophilic character.Adopt fluorescent microscope analysis to there is the dispersing characteristic of the Nano filling of fluorescent characteristic.
Compared with prior art, advantage of the present invention is the existence due to electric field, can promote the volatilization of solvent, can greatly improve film forming efficiency; Meanwhile, due to the traction of electrostatic force, inorganic nano-filler can orientation movement in film forming mother liquor, thereby can, in inversion of phases film process, be enriched in polymeric membrane surface.The high molecular nanometer composite membrane of surface enrichment mineral filler gives composite membrane more characteristic, the preparation of especially applicable surface abrasion resistance, acid and alkali-resistance, the functionalization material such as fire-resistant, luminous.
Accompanying drawing explanation
Fig. 1 is the composite membrane surface Si distribution diagram of element that comparative example 1 energy depressive spectroscopy obtains;
Fig. 2 is comparative example 1 film upper surface contact angle schematic diagram;
Fig. 3 is film deposition system schematic diagram of the present invention;
Fig. 4 is the composite membrane surface Si distribution diagram of element that the embodiment of the present invention 1 energy depressive spectroscopy obtains;
Fig. 5 is the embodiment of the present invention 1 film upper surface contact angle schematic diagram;
Fig. 6 is the composite membrane surface-element Na distribution plan that comparative example 2 energy depressive spectroscopies obtain;
Fig. 7 is film upper surface fluorescent material NaYF under comparative example 2 fluorescent microscopes
4distribution plan;
Fig. 8 is the composite membrane surface Na distribution diagram of element that the embodiment of the present invention 2 energy depressive spectroscopies obtain;
Fig. 9 is film upper surface fluorescent material NaYF under the embodiment of the present invention 2 fluorescent microscopes
4distribution plan.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
comparative example 1
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming after naturally volatilizing under room temperature, film formation time needs 24h.Matrix material is through energy spectrum analysis, and film upper surface Si content is 0.10wt%, and Si distribution diagram of element as shown in Figure 1.Contact angle is 89 °, and result as shown in Figure 2.
embodiment 1
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.54wt%, and Si distribution diagram of element as shown in Figure 4.Contact angle is 65 °, and result as shown in Figure 5.Test result is compared with comparative example 1, and inorganic nanoparticles polysilsesquioxane moves to film surface, is enriched in film surface, and surface hydrophilicity is obviously improved.
comparative example 2
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently NaYF
40.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming after naturally volatilizing under room temperature, film formation time needs 20h.Matrix material is through energy spectrum analysis, and film upper surface Na content is 0.05wt%, and Na distribution diagram of element as shown in Figure 6.Fluorescence microscopy images observation film upper surface NaYF
4as shown in Figure 7.
embodiment 2
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently NaYF
40.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 2000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Na content is 0.39wt%, and Na distribution diagram of element as shown in Figure 8.Film upper surface NaYF
4distribution plan as shown in Figure 9.Test result is compared with comparative example 2, inorganic nanoparticles NaYF
4to film surface migration, be enriched in film surface, surface fluorescence effect is strengthened.
embodiment 3
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, wherein upper plate is electronegative, lower plate earthing, and volts DS field intensity is 4000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.44wt%.
embodiment 4
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml formic acid, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 10000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.34wt%.
embodiment 5
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml trifluoroethanol, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.59wt%.
embodiment 6
The polystyrene that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml tetrahydrofuran (THF), adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.44wt%.
embodiment 7
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently polysilsesquioxane 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.74wt%.
embodiment 8
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently to cover to open up native 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 0.44wt%.
embodiment 9
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently cupric oxide 0.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surface C u content is 0.65wt%.
embodiment 10
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently Z 250 0.0005g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Fe content is 0.54wt%.
embodiment 11
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently NaYbF
40.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Na content is 0.34wt%.
embodiment 12
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml dehydrated alcohol, adds subsequently cupric oxide 0.05g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surface C u content is 0.24wt%.
embodiment 13
The polyvinyl alcohol that is 10000g/mol by 0.5g molecular weight is dissolved in 10ml deionized water, adds subsequently silicon-dioxide 0.5g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 1000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Si content is 6.5wt%.
embodiment 14
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 50ml formic acid, adds subsequently NaYF
40.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 2000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Na content is 0.69wt%.
embodiment 15
The nylon 6 that is 10000g/mol by 0.5g molecular weight is dissolved in 0.5 ml formic acid, adds subsequently NaYF
40.1g, obtains film forming mother liquor.Film forming mother liquor 5ml is placed on conduction film forming flat board, film forming flat board is placed in to parallel plate electric field, in watch-glass both sides, apply electric field, the film forming upper plate that wherein conducts electricity is electronegative, the dull and stereotyped ground connection of conduction film forming, and volts DS field intensity is 2000V.Film deposition system schematic diagram as shown in Figure 3.Under room temperature, 40min film forming liquid is separated completely the electric field action time, obtains organic/inorganic composite film.Matrix material is through energy spectrum analysis, and surperficial Na content is 0.19wt%.
Claims (10)
1. a method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler, is characterized in that concrete preparation process is as follows: (1) can be dissolved in solvent by polymer and the mineral filler of forming film with phase transformation method, prepares mother liquor; (2) mother liquor is placed on conduction film forming flat board; (3) on conduction film forming flat board, apply the electrostatic field perpendicular to conduction film forming flat board, this electrostatic field impels mother liquor inversion of phases, obtains the high molecular nanometer composite membrane of surface enrichment mineral filler.
2. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, it is characterized in that described polymer is nylon, polystyrene or polyvinyl alcohol.
3. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, it is characterized in that described solvent is trifluoroethanol, methyl alcohol, tetrahydrofuran (THF), dehydrated alcohol or deionized water.
4. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, it is characterized in that described mineral filler is polysilsesquioxane, covers and open up soil, silicon-dioxide, metal oxide or rare-earth fluorescent filler.
5. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, it is characterized in that described electrostatic field applies formation by direct supply, the voltage of described direct supply is 0V-10000V.
6. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, the polymer in the mother liquor described in it is characterized in that and the mass ratio of solvent are 0.001g/ml-10g/ml.
7. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 1, it is characterized in that mineral filler and the high molecular mass ratio in described mother liquor is 0.1%-100%.
8. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 4, it is characterized in that described metal oxide is Fe
3o
4or CuO.
9. according to a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler claimed in claim 4, it is characterized in that described rare-earth fluorescent filler is NaYF
4or NaYbF
4.
10. a kind of method of preparing the high molecular nanometer composite membrane of surface enrichment mineral filler according to claim 5, it is characterized in that conducting electricity the top of film forming flat board is provided with conduction film forming upper plate, the dull and stereotyped ground connection of described conduction film forming, described conduction film forming upper plate connects power supply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310750872.5A CN103755984B (en) | 2013-12-30 | 2013-12-30 | A kind of method of the high molecular nanometer composite membrane preparing surface enrichment inorganic filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310750872.5A CN103755984B (en) | 2013-12-30 | 2013-12-30 | A kind of method of the high molecular nanometer composite membrane preparing surface enrichment inorganic filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103755984A true CN103755984A (en) | 2014-04-30 |
| CN103755984B CN103755984B (en) | 2016-06-29 |
Family
ID=50523324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310750872.5A Active CN103755984B (en) | 2013-12-30 | 2013-12-30 | A kind of method of the high molecular nanometer composite membrane preparing surface enrichment inorganic filler |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103755984B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744930A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for improving nylon composite film surface hydrophobicity |
| CN104744715A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for preparing hydrophilic nylon film |
| CN105924954A (en) * | 2016-06-08 | 2016-09-07 | 宁波工程学院 | Preparation method of nylon CS blended membrane with high tensile strength |
| CN105936675A (en) * | 2016-06-08 | 2016-09-14 | 宁波工程学院 | Preparation method of nylon CS blend membrane |
| CN106513703A (en) * | 2016-11-22 | 2017-03-22 | 宁波工程学院 | Preparation method of chitosan Ag nano-composite film |
| CN110708945A (en) * | 2019-11-21 | 2020-01-17 | 瑞年新材料(广东)有限公司 | Light-tight film with shielding anti-interference |
| CN113861565A (en) * | 2021-11-30 | 2021-12-31 | 苏州度辰新材料有限公司 | Stiffness-increasing master batch, preparation method thereof, polyolefin film and BOPP film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453325A (en) * | 2010-10-22 | 2012-05-16 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyimide composite material with high heat conductivity |
-
2013
- 2013-12-30 CN CN201310750872.5A patent/CN103755984B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453325A (en) * | 2010-10-22 | 2012-05-16 | 东丽纤维研究所（中国）有限公司 | Preparation method of polyimide composite material with high heat conductivity |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744930A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for improving nylon composite film surface hydrophobicity |
| CN104744715A (en) * | 2015-04-03 | 2015-07-01 | 宁波工程学院 | Method for preparing hydrophilic nylon film |
| CN105924954A (en) * | 2016-06-08 | 2016-09-07 | 宁波工程学院 | Preparation method of nylon CS blended membrane with high tensile strength |
| CN105936675A (en) * | 2016-06-08 | 2016-09-14 | 宁波工程学院 | Preparation method of nylon CS blend membrane |
| CN105924954B (en) * | 2016-06-08 | 2018-07-24 | 宁波工程学院 | A kind of preparation method of high tensile nylon CS blend films |
| CN105936675B (en) * | 2016-06-08 | 2019-02-12 | 宁波工程学院 | A kind of preparation method of nylon CS blend film |
| CN106513703A (en) * | 2016-11-22 | 2017-03-22 | 宁波工程学院 | Preparation method of chitosan Ag nano-composite film |
| CN106513703B (en) * | 2016-11-22 | 2018-05-15 | 宁波工程学院 | A kind of preparation method of chitosan Ag nano composite membranes |
| CN110708945A (en) * | 2019-11-21 | 2020-01-17 | 瑞年新材料(广东)有限公司 | Light-tight film with shielding anti-interference |
| CN110708945B (en) * | 2019-11-21 | 2020-08-04 | 瑞年新材料(广东)有限公司 | Opaque film for electromagnetic shielding |
| CN113861565A (en) * | 2021-11-30 | 2021-12-31 | 苏州度辰新材料有限公司 | Stiffness-increasing master batch, preparation method thereof, polyolefin film and BOPP film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103755984B (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103755984A (en) | Method for preparing macromolecular nano composite membrane enriching inorganic filler on surface | |
| Lin et al. | Enhanced dielectric permittivity in surface-modified graphene/PVDF composites prepared by an electrospinning-hot pressing method | |
| Liu et al. | A review on mechanochemistry: Approaching advanced energy materials with greener force | |
| Kim et al. | Superior pseudocapacitive behavior of confined lignin nanocrystals for renewable energy‐storage materials | |
| Sun et al. | Microwave‐assisted in situ synthesis of graphene/PEDOT hybrid and its application in supercapacitors | |
| CN106459470B (en) | Graphene/graphite polymer composite foams derived from emulsions stabilized by graphene/graphite kinetic capture | |
| CN104157833B (en) | A kind of Graphene/titanium dioxide composite porous material and its production and use | |
| Liu et al. | Conducting and stretchable composites using sandwiched graphene-carbon nanotube hybrids and styrene-butadiene rubber | |
| Wu et al. | Novel high-hydrophilic carbon dots from petroleum coke for boosting injection pressure reduction and enhancing oil recovery | |
| Lee et al. | Stable high-capacity lithium ion battery anodes produced by supersonic spray deposition of hematite nanoparticles and self-healing reduced graphene oxide | |
| Luo et al. | Building hierarchical interfaces using BaSrTiO3 nanocuboid dotted graphene sheets in an optimized percolative nanocomposite with outstanding dielectric properties | |
| Zhang et al. | Significantly enhanced dielectric and energy storage performance of blend polymer-based composites containing inorganic 3D–network | |
| Zhou et al. | Recent advances in dispersion and alignment of fillers in PVDF-based composites for high-performance dielectric energy storage | |
| Chang et al. | like N-doped graphene films prepared by hydroxylamine diffusion induced assembly and their ultrahigh-rate capacitive properties | |
| Liu et al. | Study on energy and information storage properities of 2D-MXene/polyimide composites | |
| Li et al. | A facile approach to the fabrication of graphene-based nanocomposites by latex mixing and in situ reduction | |
| Xu et al. | High-rate, flexible all-solid-state super-capacitor based on porous aerogel hybrids of MoS2/reduced graphene oxide | |
| Simon et al. | Functionalized polystyrene maleic anhydride copolymer/ZnO nanocomposites for enhanced electrochemical performance | |
| Yang et al. | Hydroxylated graphene: A promising reinforcing nanofiller for nanoengineered cement composites | |
| Xie et al. | Perspective on interface engineering for capacitive energy storage polymer nanodielectrics | |
| Qian et al. | Enhanced mechanical and dielectric properties of natural rubber using sustainable natural hybrid filler | |
| Meng et al. | Facile preparation and electrochemical characterization of self-assembled core-shell diamond-polypyrrole nanocomposites | |
| Ishaq et al. | Synthesis of three phase graphene/titania/polydimethylsiloxane nanocomposite films and revealing their dielectric and impedance properties | |
| Guan et al. | Preparation and electrochemical performance of activated carbon microspheres from recycled novolak phenol formaldehyde | |
| Patil et al. | An all chemical route to design a hybrid battery-type supercapacitor based on ZnCo2O4/CdS composite nanostructures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |