CN107955307A - Silica/magnesia/polymer composite dielectric hydrophobic material and preparation method - Google Patents
Silica/magnesia/polymer composite dielectric hydrophobic material and preparation method Download PDFInfo
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- CN107955307A CN107955307A CN201711240863.6A CN201711240863A CN107955307A CN 107955307 A CN107955307 A CN 107955307A CN 201711240863 A CN201711240863 A CN 201711240863A CN 107955307 A CN107955307 A CN 107955307A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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Abstract
The present invention relates to nanocomposite technical field, it is desirable to provide a kind of silica/magnesia/polymer composite dielectric hydrophobic material and preparation method.The dielectric hydrophobic material is using polymethyl methacrylate as polymeric matrix, using the magnesia for the shell that is coated with silicon oxide as packing material, is made by blending, tape casting；The packing material accounts for the 10%~40% of dielectric hydrophobic material gross mass, and for packing material using silica as shell, its stratum nucleare is sheet magnesia.The present invention can increase between inorganic particle, inorganic particle/polymer interface interaction zone, realize that interfacial polarization effect strengthens, improve the dielectric constant of composite material, while improve hydrophobic properties of the surface.Preparation process of the present invention is simple, and the operability and repeatability of method are high.By adjusting the addition content of inorganic filler, the performance regulation and control such as the dielectric of composite material, calorifics, hydrophobic are realized, can be applied to capacitor, the manufacture for the device such as electrowetting is shown, there is vast potential for future development.
Description
Technical field
The present invention relates to a kind of silica/magnesia/polymer composite dielectric hydrophobic material and preparation method, belong to and receive
Nano composite material technical field.
Background technology
On dielectric dielectric wetting be a kind of control technology to miniature droplets, be widely used in display, optics,
The fields such as medical treatment, microfluid.In numerous microlayer model control technologies, it is that one kind utilizes voltage manipulation droplet of ink that electrowetting, which is shown,
Sprawl with aggregation the New Type Display Devices show.Compared to other display devices, electrowetting, which is shown, combines electronics
The controllability of display and the reflecting display principles of traditional paper, have excellent and unique advantages for development.
Dielectric layer is particularly critical in electric moistening display part one layer, in addition to insulating properties, it is also necessary to possesses higher Jie
Electric constant and hydrophobic properties of the surface.The dielectric constant of dielectric floor height can suitably reduce the startup voltage of display device.Current big portion
Divide the dielectric constant of hydrophobic polymer relatively low (being less than 3), cause startup voltage higher, effective drive needed for all kinds of Electrowetting devices
Dynamic voltage is in 50~150V.So high driving voltage, not only limit integrated application, also easily cause dielectric layer breakdown and
The ionization of drop, reduces the stability of device；And high Jie's inorganic material can not take into account hydrophobic property, reduce electric in display device
Press the control to drop.To solve the problems, such as this, researchers are typically employed in dielectric layer surface and coat one layer of hydrophobic layer with same
When meet the requirement of dielectric constant and hydrophobic performance.But double membrane structure is not only complicated, manufacturing cost is added, and
It is generally necessary to special Preparation equipment, such as chemical vapor deposition, atomic deposition.These equipment are also with higher preparation
Temperature, higher requirement is proposed to preparing environment.
Polymethyl methacrylate, also known as organic glass, are one of widely used polymer, are possessed higher tough
Property and stronger toughness, dissolve in organic solvent, easily prepared to mold micron order film, suitable for mass production.But it is situated between
Electrical property and hydrophobic performance are all slightly insufficient, limit its application in fields such as capacitance, electrowettings.
The content of the invention
The problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of silica/magnesia/poly-
Compound composite dielectric hydrophobic material and preparation method.
To solve technical problem, the technical solution adopted in the present invention is：
There is provided a kind of silica/magnesia/polymer composite dielectric hydrophobic material, it is characterised in that the dielectric is hydrophobic
Material be using polymethyl methacrylate as polymeric matrix, using the magnesia for the shell that is coated with silicon oxide as packing material,
It is made by blending, tape casting；The packing material accounts for the 10%~40% of dielectric hydrophobic material gross mass, packing material with
Silica is shell, its stratum nucleare is sheet magnesia.
The present invention has further put forward the preparation method of the dielectric hydrophobic material, comprises the following steps：
(1) in mass ratio 1: 10 polymethyl methacrylate is added in n,N-Dimethylformamide, mixes, stirs at room temperature
Mix to clarification；Then the magnesia packing material for the shell that is coated with silicon oxide is disperseed in the solution, to obtain uniform suspended
Liquid；
(2) suspension is molded through casting machine, is molded when drying 24 is small in 60 DEG C of vacuum drying ovens, obtains film-form
Silica/magnesia/polymer composite dielectric hydrophobic material；
In step (1), the additive amount of packing material is controlled, it is accounted for dielectric hydrophobic material gross mass after shaping
10%~40%.
In the present invention, being separated into described in step (1)：12h is stirred at room temperature after ultrasonic disperse 2h.
In the present invention, the packing material is prepared by following methods：
(1) sheet magnesium oxide dispersion is obtained into magnesium oxide dispersion liquid in ethanol, 60ml ethanol is added per 1g magnesia；So
After sequentially add ammonium hydroxide, tetraethyl orthosilicate and deionized water, be stirred at room temperature reaction 6 it is small when；
Reactant is to be added into 1.5ml ammonium hydroxide, 0.8ml tetraethyl orthosilicates and 4ml deionization water controls by every 1 gram of magnesia
Additive amount processed；Wherein, ammonium hydroxide with tetraethyl orthosilicate is added dropwise in the form of respective ethanol dilution, ammonia in dilution
Water is 1 with ethanol volume ratio:10, ethyl orthosilicate is 1 with ethanol volume ratio:12.5；
(2) after when reaction 6 is small, it is centrifugally separating to obtain product；Washed repeatedly with ethanol, move to 60 DEG C of oven dried overnights,
Obtain the magnesia of the shell that is coated with silicon oxide as packing material.
In the present invention, the sheet magnesia is prepared by following methods：
(1) in the stainless steel cauldron with polytetrafluoroethylliner liner, by magnesium chloride hexahydrate and polyvinylpyrrolidone
It is dissolved in deionized water, stirs to solution and clarify at room temperature；Ammonium hydroxide is added dropwise into settled solution, in 180 DEG C of guarantors after stirring
When temperature 3 is small；
Wherein, every gram of magnesium chloride hexahydrate is dissolved in 15ml deionized waters；Magnesium chloride hexahydrate and polyvinylpyrrolidone
Mass ratio is 4: 1, and the molar ratio of magnesium chloride hexahydrate and ammonium hydroxide is 1: 2；
(2) after reaction, cooled to room temperature；Centrifuge and obtain product, and number is alternately washed with second alcohol and water
It is secondary, when 60 DEG C of dryings 24 are small, obtain presoma magnesium hydroxide；
(3) when by presoma magnesium hydroxide, calcination 3 is small in atmosphere, calcination temperature is 500 DEG C, obtains sheet magnesia.
In the present invention, described in the step (1) be separated into ultrasonic disperse 30min after stir 30min.
Inventive principle describes：
The present invention adds poly- methyl-prop by using appropriate method using the bitter earth nano particle after cladding as filler
In e pioic acid methyl ester, laminated film is prepared.It is mutual using a large amount of interfaces introduced between inorganic particle, between inorganic particle/polymer
Effect, significantly improves interfacial polarization effect, while take into account calorifics, hydrophobic properties of the surface.
Compared with prior art, the advantage of the invention is that：
1st, the bitter earth nano piece of pattern and size uniformity is prepared by hydro-thermal method, and by teos hydrolysis,
The amorphous silica in uniform thickness in mgo surface cladding.Prepared by solution blending, tape casting containing bag
Cover the thin polymer film of magnesia particle.The composite material of structure can increase between inorganic particle, inorganic particle/polymer interface phase
Interaction region, realizes that interfacial polarization effect strengthens, improves the dielectric constant of composite material, while improve hydrophobic properties of the surface.
2nd, preparation process of the present invention is simple, and the operability and repeatability of method are high.By adjusting adding for inorganic filler
Add content, realize the performance regulation and control such as the dielectric of composite material, calorifics, hydrophobic, can be applied to capacitor, the device such as electrowetting is shown
Manufacture, there is vast potential for future development.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph of magnesia.
Wherein, it is sheet magnesia SEM photograph prepared in embodiment to scheme (a) and (b), and figure (c) and (d) are respectively piece
Shape magnesia and the magnesia TEM photos being coated with silicon oxide.
Fig. 2 is XRD spectrum and the XPS figure of magnesia and coated magnesium oxide.
Wherein, the XRD spectrum of (a) for sheet magnesia and coated magnesium oxide prepared in embodiment is schemed, figure (b) is real
Apply the XPS figures of sheet magnesia prepared in example and coated magnesium oxide.
Embodiment
With reference to embodiment and comparative example, the invention will be further described, and embodiment can make the professional skill of this specialty
The present invention, but do not limit the invention in any way is more fully understood in art personnel.
Embodiment 1-4
(1) 60ml deionized waters, six water chlorine of 4g are added into the 100ml stainless steel cauldrons with polytetrafluoroethylliner liner
Change magnesium, 1g polyvinyl pyrrolidones, 3ml ammonium hydroxide is added dropwise to after clarifying in agitating solution at room temperature, and stirring seals after 5 minutes,
Move into air dry oven when 180 DEG C of insulations 3 are small.
(2) after reaction, cooled to room temperature；Centrifuge and obtain white precipitate, handed over deionized water and ethanol
For washing for several times, move to 60 DEG C of dryings 24 of drying box it is small when, obtain presoma magnesium hydroxide.
(3) when by presoma magnesium hydroxide, calcination 3 is small in atmosphere, calcination temperature is 500 DEG C, obtains white oxide magnesium powder
End (its micro-shape in the form of sheets, such as Fig. 1).
(4) obtained sheet magnesia in step (3) is taken into 1g, ultrasonic disperse is in 60ml ethanol.By 0.8ml/10ml
The ethanol dilution of ethyl orthosilicate, the ethanol dilution of 1.5ml/15ml ammonium hydroxide and 4ml deionized waters, are added dropwise magnesia
In dispersion liquid, reacted when stirring 6 is small at room temperature.
(5) after the reaction was complete, white precipitate is centrifugally separating to obtain, 60 DEG C of oven drying mistakes are moved to after ethanol washing for several times
Night, the magnesium oxide particle for the shell that obtains being coated with silicon oxide.
(6) polymethyl methacrylate is added to n,N-Dimethylformamide, wherein n,N-Dimethylformamide is with adding
Polymethyl methacrylate mass ratio be 10:1.After mixed liquor stirs to clarify, it is coated with silicon oxide what is be prepared
The magnesia packing material of shell is dispersed in settled solution, obtains uniform suspension.
(7) suspension is molded through casting machine, is molded when drying 24 is small in 60 DEG C of vacuum drying ovens, after solvent volatilization
Obtain required silica/magnesia/polymer composite film (i.e. silica/magnesia/hydrophobic material of polymer composite dielectric
Material), numbering is as shown in table 1.
In step (6), the additive amount of packing material is controlled, it is accounted for dielectric hydrophobic material gross mass after shaping
10%~40%.
(8) it is 100nm to plate thickness respectively on composite membrane two sides by vacuum coating equipment, and a diameter of 20mm fine copper is as electricity
Pole, carries out follow-up electrical performance testing.
Comparative example (embodiment 5-7)
(1) by polymethyl methacrylate according to 1:10 are dissolved in n,N-Dimethylformamide, and solution stirs to clarify
After add magnesium oxide powder, magnesia filling quality fraction is 40%.Numbering MS-40 samples add magnesia as the sheet prepared
Magnesium oxide powder；Numbering MC-40 samples are addition commercial particulate shape magnesia (50nm, Aladdin).
(2) by polymethyl methacrylate according to 1:5 are dissolved in n,N-Dimethylformamide, and solution is stirred until homogeneous clear
Clearly, sample number into spectrum M-0.
(3) by sample MS-40, MC-40, M-0 after casting machine tape casting, 60 DEG C of vacuum drying of vacuum drying chamber are moved to
24h, obtains control group magnesia/polymethyl methacrylate film and pure PMMA films.
(4) it is 100nm to plate thickness respectively on composite membrane two sides by vacuum coating equipment, and a diameter of 20mm fine copper is as electricity
Pole, carries out follow-up electrical performance testing.
Implementation result compares
The SEM figures that Fig. 1 (a) and (b) are MgO prepared by the present invention, it can be seen that the MgO prepared in the form of sheets, size uniformity,
Grain size is 0.5-1 μm, and thickness is measured as 25nm or so through AFM.Scheme in TEM under (Fig. 1 (c)) it can be seen that bitter earth nano
Piece surface increases the specific surface area of magnesia there are gully.It is original that Fig. 1 (d) then significantly illustrates that magnesia maintains
The uniform silica shell that sheet-like morphology and surface successfully coat, thickness are about 25-30nm.
Fig. 2 (a) is sheet MgO and SiO prepared by the present invention respectively2The XRD spectrum of@MgO, as can be seen from the figure prepares
MgO crystal forms be Emission in Cubic magnesia (PDF#45-0946), and SiO2Do not see obvious peak intensity, occur in low angle non-
Brilliant peak, the silica for illustrating cladding is amorphous silica.Fig. 2 (b) is the XPS collection of illustrative plates of two kinds of powder, for proving
SiO2Presence.
Table 1 gives the test performance of the laminated film that example is prepared in embodiment and comparative example.Can be with from table
Find out, the dielectric constant of laminated film is with SiO2The rise of@MgO filling fractions and raise.Work as SiO2@MgO filling quality fractions
For 40% when, the dielectric constant of composite material is 14.6, is 4 times of pure polymer.Under identical filling fraction, sheet oxidation
Magnesium/polymer composites dielectric constant is 8.54, and commercial magnesia/polymer composites dielectric constant is 6.48.Dioxy
Lifting of the introducing of SiClx layer to dielectric constant plays an important roll：On the one hand, the dielectric constant of silica is between magnesia
Between polymethyl methacrylate, play the role of dielectric buffer layer.On the other hand, the introducing of silicon dioxide layer greatly increases
Composite material interface, significantly increases interfacial polarization effect, is conducive to the raising of dielectric constant.In addition, sample contact angle also with
The rise of filler particles content and raise, highest can reach 115 °.Mother glass conversion temperatures all at the same time are respectively less than
120 °, meet the requirement of the follow-up preparation process of electric moistening display part.
Table 1
It should be noted that above-described embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition
It is to be understood that after reading the content taught by the present invention, those skilled in the art can make the present invention various changes or repair
Change, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (6)
1. a kind of silica/magnesia/polymer composite dielectric hydrophobic material, it is characterised in that the dielectric hydrophobic material is
Using polymethyl methacrylate as polymeric matrix, using the magnesia for the shell that is coated with silicon oxide as packing material, by altogether
Mixed, tape casting is made；The packing material accounts for the 10%~40% of dielectric hydrophobic material gross mass, and packing material is with titanium dioxide
Silicon is shell, its stratum nucleare is sheet magnesia.
2. the preparation method of dielectric hydrophobic material described in claim 1, it is characterised in that comprise the following steps：
(1) in mass ratio 1: 10 polymethyl methacrylate is added in n,N-Dimethylformamide, mixes, stirred extremely at room temperature
Clarification；Then the magnesia packing material for the shell that is coated with silicon oxide is disperseed in the solution, to obtain uniform suspension；
(2) suspension is molded through casting machine, is molded when drying 24 is small in 60 DEG C of vacuum drying ovens, obtains the two of film-form
Silica/magnesia/polymer composite dielectric hydrophobic material；
In step (1), control the additive amount of packing material, make its account for shaping after dielectric hydrophobic material gross mass 10%~
40%.
3. according to the method described in claim 2, it is characterized in that, being separated into described in step (1)：Ultrasonic disperse 2h rear chambers
Temperature stirring 12h.
4. the method according to claims 2 or 3, it is characterised in that the packing material is prepared by following methods and obtained
：
(1) sheet magnesium oxide dispersion is obtained into magnesium oxide dispersion liquid in ethanol, 60ml ethanol is added per 1g magnesia；Then according to
Secondary addition ammonium hydroxide, tetraethyl orthosilicate and deionized water, be stirred at room temperature reaction 6 it is small when；
Reactant is to be added into 1.5ml ammonium hydroxide, 0.8ml tetraethyl orthosilicates and the control of 4ml deionized waters by every 1 gram of magnesia to add
Dosage；Wherein, ammonium hydroxide with tetraethyl orthosilicate is added dropwise in the form of respective ethanol dilution, in dilution ammonium hydroxide with
Ethanol volume ratio is 1:10, ethyl orthosilicate is 1 with ethanol volume ratio:12.5；
(2) after when reaction 6 is small, it is centrifugally separating to obtain product；Washed repeatedly with ethanol, move to 60 DEG C of oven dried overnights, to obtain the final product
To the magnesia of the shell that is coated with silicon oxide as packing material.
5. according to the method described in claim 4, it is characterized in that, the sheet magnesia is prepared by following methods：
(1) in the stainless steel cauldron with polytetrafluoroethylliner liner, magnesium chloride hexahydrate and polyvinylpyrrolidone are dissolved in
In deionized water, stir to solution and clarify at room temperature；Ammonium hydroxide is added dropwise into settled solution, it is small in 180 DEG C of insulations 3 after stirring
When；
Wherein, every gram of magnesium chloride hexahydrate is dissolved in 15ml deionized waters；The quality of magnesium chloride hexahydrate and polyvinylpyrrolidone
Than for 4: 1, the molar ratio of magnesium chloride hexahydrate and ammonium hydroxide is 1: 2；
(2) after reaction, cooled to room temperature；Centrifuge and obtain product, and with the washing of second alcohol and water alternating for several times,
When 60 DEG C of dryings 24 are small, presoma magnesium hydroxide is obtained；
(3) when by presoma magnesium hydroxide, calcination 3 is small in atmosphere, calcination temperature is 500 DEG C, obtains sheet magnesia.
6. according to the method described in claim 4, it is characterized in that, it is separated into ultrasonic disperse described in the step (1)
30min is stirred after 30min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087032A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silicon oxide and magnesium oxide composite material and synthesis method thereof |
| CN111138769A (en) * | 2019-12-05 | 2020-05-12 | 常州聚焦橡塑新材料有限公司 | Preparation process of non-vulcanized butyl rubber |
| CN112742341A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Magnesium oxide-silicon oxide composite with core-shell structure and preparation method thereof |
| CN114512341A (en) * | 2022-03-10 | 2022-05-17 | 常州工学院 | Ultralow filler and high-energy-storage-density dielectric material for energy storage capacitor and preparation method thereof |
| CN114948907A (en) * | 2022-04-19 | 2022-08-30 | 张楠 | MgO @ SiO with core-shell structure 2 Nano capsule and preparation method thereof |
| CN114512341B (en) * | 2022-03-10 | 2024-07-30 | 常州工学院 | Dielectric material with ultralow filler and high energy storage density for energy storage capacitor and preparation method of dielectric material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087032A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silicon oxide and magnesium oxide composite material and synthesis method thereof |
| CN112742341A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Magnesium oxide-silicon oxide composite with core-shell structure and preparation method thereof |
| CN112742341B (en) * | 2019-10-30 | 2024-05-31 | 中国石油化工股份有限公司 | Core-shell structure magnesium oxide-silicon oxide complex and preparation method thereof |
| CN111138769A (en) * | 2019-12-05 | 2020-05-12 | 常州聚焦橡塑新材料有限公司 | Preparation process of non-vulcanized butyl rubber |
| CN111138769B (en) * | 2019-12-05 | 2022-03-22 | 常州聚焦橡塑新材料有限公司 | Preparation process of non-vulcanized butyl rubber |
| CN114512341A (en) * | 2022-03-10 | 2022-05-17 | 常州工学院 | Ultralow filler and high-energy-storage-density dielectric material for energy storage capacitor and preparation method thereof |
| CN114512341B (en) * | 2022-03-10 | 2024-07-30 | 常州工学院 | Dielectric material with ultralow filler and high energy storage density for energy storage capacitor and preparation method of dielectric material |
| CN114948907A (en) * | 2022-04-19 | 2022-08-30 | 张楠 | MgO @ SiO with core-shell structure 2 Nano capsule and preparation method thereof |
| CN114948907B (en) * | 2022-04-19 | 2023-08-08 | 张楠 | MgO@SiO with core-shell structure 2 Nanocapsules and method for preparing the same |
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