CN108517583A - A kind of preparation method of gallic acid zinc nano-fiber material - Google Patents
A kind of preparation method of gallic acid zinc nano-fiber material Download PDFInfo
- Publication number
- CN108517583A CN108517583A CN201810394392.2A CN201810394392A CN108517583A CN 108517583 A CN108517583 A CN 108517583A CN 201810394392 A CN201810394392 A CN 201810394392A CN 108517583 A CN108517583 A CN 108517583A
- Authority
- CN
- China
- Prior art keywords
- gallic acid
- nanofiber
- acid zinc
- solution
- preparation
- 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
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
Abstract
The present invention relates to nano material preparation research fields, and in particular to a kind of preparation method of gallic acid zinc nano-fiber material.The preparation method that the present invention is combined using collosol and gel, electrostatic spinning and heat treatment sintering.Nanofiber diameter is about in 100nm.It is prepared using method of electrostatic spinning, the gallic acid zinc nanofiber of preparation has one-dimensional crystal structure, and purity is high, and controllability is good, has fine near-infrared luminous performance, and there is good application prospect in the fields such as imaging, drug gene carrier in vivo.The preparation method equipment of the present invention is simple, and has easy control of process conditions, and of low cost, yield is big, the advantages that being easy to industrialized production.
Description
Technical field
The invention belongs to inorganic nano-fiber field of material technology, are related to a kind of preparation side of gallic acid zinc nano-fiber material
Method.
Background technology
Inorganic nano medicament carrier system has various advantages relative to organic nano medicament carrier system, such as
It has accurate regulatable appearance and size, can selectivity be gathered in lesions position；Chemical stabilization is good, can be with the long period
It recycles in vivo, extended treatment time and effect；Has many characteristics, such as unique optics, magnetics, electricity, acoustics, for biological group
It is made into picture or the intellectual drug carrier system of environmental stimuli response.In general, inorganic light-emitting system can be significantly improved by doping
The optical property of system.Most doping luminescent systems is mostly the up-conversion luminescence with rare earth element (such as group of the lanthanides, actinium series) at present
System, and the intrinsic toxicity of rare earth element cannot be ignored, the advantage of non-rare earth doping (such as transition metal) is just shown
Come.Transition metal element Cr3+Be chromium it is the essential trace elements of the human body, it is normal growth and development and adjusts the important of blood glucose
Element.Cr3+The ZnGa of doping2O4The near infrared light transmitting of higher purity and brightness can be generated after material excitation, simultaneously because
ZnGa2O4It is widely used in technical field of biological material with good describing property of biology, is based on ZnGa2O4Biomedical material
All it is one including being imaged and treating etc. and has very much promising research direction.
Intelligent topical remedy's carrier system (such as in affected site patch last layer nano fibrous membrane) is a kind of promising
Drug delivery therapeutic strategy.It is by compared with conventional drug delivery system, and local medicine-applying system can keep lower whole body medicine
Object concentration, avoids the side effect of drug systemic circulation brought, while ensuring the medicine dosage in lesions position for a long time,
The repeated multiple times administration of convenient administration system is avoided, therapeutic effect is improved.This gallic acid zinc nanofiber pastes after carrying drug
In affected site, dosage can be improved by the one hand improving, on the other hand can with response external exciting light, provide it is lasting, can
Control and programmable drug release, reaches therapeutic effect.
Electrostatic spinning technique be based on collosol and gel, using high-voltage electrostatic field formed Coulomb force to spinning solution carry out stretch and
Injection, rapid desiccation forms nanofiber to the spinning solution to be stretched in air.Electrospinning process equipment is simple, technology
Flexibly, suitable material range is wide, and fiber obtained is continuous, draw ratio is big, controlled diameter, yield are high therefore micro-nano preparing
Fiber art has excellent development prospect.
Invention content
The object of the present invention is to provide a kind of gallic acid zinc nano-fiber material and preparation method thereof, in conjunction with sol-gal process,
Using advanced high-voltage electrostatic spinning apparatus, size uniformity, the nanofiber with high draw ratio are prepared.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of gallic acid zinc nano-fiber material and its preparation side
Method includes the following steps：
(1) being uniformly mixed 2mL deionized waters, 6mL ethanol solutions and 3mLDMF, magnetic agitation is half small at room temperature
When, mixing speed 300-500rpm forms the solution 1 of stable homogeneous.
(2) by 0.475g gallium nitrates (Ga (NO3)3·xH2O), 0.279g zinc nitrates (Zn (NO3)3·6H2) and 0.002g O
Chromic nitrate (Cr (NO3)3·9H2O it) is dissolved into solution 1, stirs 1h at room temperature, obtain stable solution 2.(each metal ion species
Molar ratio be Zn:Ga:Cr=1:1.995:0.005, i.e. Cr3+Doping be 0.5%)
(3) it weighs 0.7gPVP to be added in solution 2, stirs 3h, obtain uniform precursor solution.
(4) electrostatic spinning apparatus for utilizing flat panel collector, gallic acid zinc nanofiber is made by precursor solution, wherein spray
Silk head is 15cm, feeding speed 0.15-0.2mL/h, spinning voltage 8-10kV at a distance from reception substrate.
(5) by the gallic acid zinc nanofiber of collection in 37 DEG C of oven dryings.
(6) by step (5), treated that strontium titanates nanofiber is put into tube furnace, with the heating rate liter of 10 DEG C/min
Temperature keeps the temperature 6 hours after annealings to 800 DEG C, forms gallic acid zinc nanofiber, at room temperature kept dry.
The present invention regulates and controls the stability of electrospinning presoma by changing collosol and gel preparation parameter, collected by regulation and control
The size and shape of gallic acid zinc nanofiber.The present invention is using the simple mechanism of uniaxial electrospinning, and solvent volatilizees in electro-spinning process,
It can be obtained the one-dimensional gallic acid zinc nanofiber of pure phase after the reaction was complete as the PVP of spinning-aid agent in sintering process simultaneously.Compared with
The good crystalline material of crystal property is obtained after the heat treatment of high temperature.Using the method for electrostatic spinning simply based on collosol and gel,
It is prepared for that purity is high, the gallic acid zinc nanofiber with one-dimensional crystal structure of stable structure.The electrostatic spinning gallic acid of the present invention
Zinc nanofiber process equipment is simple, of low cost, and fibre diameter is uniform, is produced on a large scale.
Description of the drawings
Fig. 1 is the taylor cone for stablizing jet stream in electro-spinning process using the formation of high speed camera shooting.
Fig. 2 is to utilize the 0.5%Cr prepared after sol-gal process, electrostatic spinning and sintering3+Adulterate gallic acid zinc (ZnGa2O4：
Cr) SEM, TEM photo of nanofiber and EDC elemental analysis power spectrums, a in corresponding diagram 2, b, c scheme respectively.
Fig. 3 is the 0.5%Cr3+The XRD spectrum for adulterating gallic acid zinc nanofiber, it is vertical with standard card PDF#38-1024
Square phase ZnGa2O4It matches.
Fig. 4 is the 0.5%Cr3+Adulterate the excitation spectrum and emission spectrum of gallic acid zinc nanofiber.(a) figure is 696nm hairs
Penetrate the excitation spectrum under light detection；(b) emission spectrum under the exciting light for being 560nm.
Fig. 5 is the 0.5%Cr3+Adulterate gallic acid zinc nanofiber MTT cytotoxicity experiments, cell survival rate 90% with
On.
Specific implementation mode
It is further illustrated the present invention below in conjunction with attached drawing and specific example.
Example 1：Probe into influence of the spinning-aid agent PVP dosages to electrospinning precursor solution stability
(1) being uniformly mixed 2mL deionized waters, 6mL ethanol solutions and 3mLDMF, magnetic agitation is half small at room temperature
When, mixing speed 300-500rpm forms the solution 1 of stable homogeneous.
(2) by 0.475g gallium nitrates (Ga (NO3)3·xH2O), 0.279g zinc nitrates (Zn (NO3)3·6H2) and 0.002g O
Chromic nitrate (Cr (NO3)3·9H2O it) is dissolved into solution 1, stirs 1h at room temperature, obtain stable solution 2.(each metal ion species
Molar ratio be Zn:Ga:Cr=1:1.995:0.005, i.e. Cr3+Doping be 0.5%)
(3) 0.5g, 0.6g, 0.7g and 0.8g PVP are weighed respectively to be added in solution 2, stir 3h, obtain uniform forerunner
Liquid solution 1,2,3 and 4.
(4) electrostatic spinning apparatus for utilizing flat panel collector, gallic acid zinc nanometer is respectively prepared by precursor solution 1,2,3 and 4
Fiber, wherein spinning head is 15-20cm at a distance from reception substrate, and adjusting feeding speed is 0.1-0.5mL/h, adjusts spinning
Voltage is 7-15kV.Selecting, which can carry out stablizing electrospinning parameters, carries out subsequent experimental.
1 conclusion of example：During electrostatic spinning, the concentration and viscosity of solution have decision to the diameter and pattern of spinning
Property influence.When PVP additions are smaller, viscosity is too low, can not form continuity spinning；When the addition of PVP crosses major issue, viscosity
Excessive, the stress relaxation time of Polymer Solution is longer, this will influence the division of jet stream.Only suitable addition could be steady
Determine electrospinning, this when, the addition of PVP was 0.7g.
Example 2：Probe into influence of each component ratio of solvent to electrospinning precursor solution stability
(1) deionized water, ethanol solution and DMF are uniformly mixed respectively by the parameter in table one, at room temperature magnetic agitation
Half an hour, mixing speed 300-500rpm form the solution 1 of stable homogeneous.
(2) by 0.475g gallium nitrates (Ga (NO3)3·xH2O), 0.279g zinc nitrates (Zn (NO3)3·6H2) and 0.002g O
Chromic nitrate (Cr (NO3)3·9H2O it) is dissolved into solution 1, stirs 1h at room temperature, obtain stable solution 2.(each metal ion species
Molar ratio be Zn:Ga:Cr=1:1.995:0.005, i.e. Cr3+Doping be 0.5%)
(3) 0.7g PVP are weighed to be added in solution 2, stirs 3h, obtains uniform precursor solution.
(4) electrostatic spinning apparatus for utilizing flat panel collector, gallic acid zinc nanofiber is made by precursor solution, wherein spray
Silk head is 15-20cm at a distance from reception substrate, and adjusting feeding speed is 0.15-0.4mL/h, and adjusting spinning voltage is 7-
12kV.Selecting, which can carry out stablizing electrospinning parameters, carries out subsequent experimental.
Table one
| Experimental group | PVP | Ethyl alcohol | DMF | Deionized water |
| 2-1 | 0.7g | 3ml | 3ml | 5ml |
| 2-2 | 0.7g | 4ml | 4ml | 3ml |
| 2-3 | 0.7g | 5ml | 4ml | 2ml |
| 2-4 | 0.7g | 5ml | 5ml | 1ml |
| 2-5 | 0.7g | 6ml | 3ml | 2ml |
| 2-6 | 0.7g | 6ml | 2ml | 3ml |
| 2-7 | 0.7g | 7ml | 2ml | 2ml |
2 conclusion of example：Under conditions of spinning-aid agent PVP and certain total solvent volume amount, solvent composition is influenced than regular meeting
The surface tension of electrospinning precursor solution, to influence the stability of electrospinning.During electrostatic spinning, the size of surface tension is determined
The spinning that product is drop, the silk with pearl node or uniform diameter is determined, if can be under lower operation voltage
Start electrospinning.With the increasing of ethanol consumption, electrospinning is gradually intended to stablize.The ratio of DMF and water probes into middle discovery, DMF's
When dosage is more than water, stable electrospinning can be more carried out.The experimental group of 2-5 can form stable taylor cone, be final solvent
Proportioning.
Example 3：Probe into influence of the ion concentration to electrospinning precursor solution stability
(1) being uniformly mixed 2mL deionized waters, 6mL ethanol solutions and 3mLDMF, magnetic agitation is half small at room temperature
When, mixing speed 300-500rpm forms the solution 1 of stable homogeneous.
(2) by gallium nitrate (Ga (NO3)3·xH2O), zinc nitrate (Zn (NO3)3·6H2) and chromic nitrate (Cr (NO O3)3·
9H2O it) is dissolved into solution 1 by the proportioning of table two, stirs 1h at room temperature, obtain stable solution 2.(each metal ion species rub
You are than being Zn:Ga:Cr=1:1.995:0.005, i.e. Cr3+Doping be 0.5%)
(3) 0.7g PVP are weighed to be added in solution 2, stirs 3h, obtains uniform precursor solution.
(4) electrostatic spinning apparatus for utilizing flat panel collector, gallic acid zinc nanofiber is made by precursor solution, wherein spray
Silk head is 15-20cm at a distance from reception substrate, and adjusting feeding speed is 0.15-0.4mL/h, is adjusted
Section spinning voltage is 7-12kV.Selecting, which can carry out stablizing electrospinning parameters, carries out subsequent experimental.
Table two
| Experimental group | Ga(NO3)3·xH2O | Zn(NO3)3·6H2O | Cr(NO3)3·9H2O |
| 3-1 | 0.238g | 0.139g | 0.001g |
| 3-2 | 0.475g | 0.279g | 0.002g |
| 3-3 | 0.950g | 0.558g | 0.004g |
3 conclusion of example：Under conditions of spinning-aid agent PVP and solvent composition and certain dosage, the addition of salting liquid can shadow
The conductivity for ringing electrospinning precursor solution, to influence the stability of electrospinning fibre.When the conductivity of solution is relatively low, electricity can be caused
It can contain pearl node in the spinning that the jet stream that field force is drawn cannot fully be extended, therefore be obtained.And when the addition mistake of inorganic salts
Oversaturated salting liquid is formed when high, cannot equally form stable electrospinning.Experiment finds that 3-2 groups can form stable electricity
It spins.
Example 4：It chooses stable electrospinning parameters condition and carries out sample collection and performance test
(1) being uniformly mixed 2mL deionized waters, 6mL ethanol solutions and 3mLDMF, magnetic agitation is half small at room temperature
When, mixing speed 300-500rpm forms the solution 1 of stable homogeneous.
(2) by 0.475g gallium nitrates (Ga (NO3)3·xH2O), 0.279g zinc nitrates (Zn (NO3)3·6H2) and 0.002g O
Chromic nitrate (Cr (NO3)3·9H2O it) is dissolved into solution 1, stirs 1h at room temperature, obtain stable solution 2.(each metal ion species
Molar ratio be Zn:Ga:Cr=1:1.995:0.005, i.e. Cr3+Doping be 0.5%)
(3) it weighs 0.7gPVP to be added in solution 2, stirs 3h, obtain uniform precursor solution.
(4) electrostatic spinning apparatus for utilizing flat panel collector, gallic acid zinc nanofiber is made by precursor solution, wherein spray
Silk head is 15cm, feeding speed 0.15-0.2mL/h, spinning voltage 8-10kV at a distance from reception substrate.With Germany
Baumer company's T XG04h high speed cameras take the taylor cone that can form stable electrospinning, as shown in Figure 1.
(5) by the gallic acid zinc nanofiber of collection in 37 DEG C of oven dryings.
(6) by step (5), treated that strontium titanates nanofiber is put into tube furnace, with the heating rate liter of 10 DEG C/min
Temperature keeps the temperature 6 hours after annealings to 800 DEG C, forms gallic acid zinc nanofiber, at room temperature kept dry.
(7) the gallic acid zinc nanofiber of gained observation is carried out with Quanta 650FEG types scanning electron microscope to take pictures,
As a result it is Fig. 2 a, it can be seen that prepared nanofiber diameter is in 100 rans.It is saturating with Tecnai G2F20S-TWIN types
It penetrates electron microscope and carries out observation and take pictures, and carry out High Resolution Observations its lattice fringes, as a result as shown in Figure 2 b, it can be seen that institute
The nanofiber of preparation is polycrystalline fibre, and crystallinity is fine.The EDC power spectrum elemental analyses of Fig. 2 c confirm the gallic acid zinc Nanowire
The presence of Zn, Ga, O, Cr element in dimension.Object phase point is carried out with Japanese Rigaku companies D/max2200PC types X-ray diffractometer
Analysis, the results are shown in Figure 3, the preferable gallic acid zinc nanofiber crystal of crystallinity is obtained, with standard card PDF#38-1024 pure phases
Gallic acid zinc match, belong to cubic system.Spectrum test is carried out with FLS920 type Cryogenic Temperature Swing all band Fluorescence Spectrometer, is obtained
To the exciting light spectrogram 4a and launching light spectrogram 4b of the fiber.Broad peak of the fiber near infrared region (600-800nm) emits,
In 700nm or so, there are two strong emission peaks (696nm and 709nm).Cytotoxicity experiment is carried out to the gallic acid zinc nanofiber, such as
Shown in Fig. 5.It is laggard that the gallic acid zinc fiber and cell of various concentration (25,50,75 and 100 μ g/ml) cultivate 24,48 and 72h respectively
Row MTT tests, cell survival rate is 90% or more, it was demonstrated that the nanofiber has good biocompatibility, has good
Biologic applications foreground.
Claims (5)
1. a kind of preparation method of gallic acid zinc nano-fiber material, which is characterized in that this approach includes the following steps：
(1) being uniformly mixed 2mL deionized waters, 6mL ethanol solutions and 3mLDMF, at room temperature magnetic agitation half an hour, shape
At the solution 1 of stable homogeneous.
(2) by 0.475g gallium nitrates (Ga (NO3)3·xH2O), 0.279g zinc nitrates (Zn (NO3)3·6H2) and 0.002g nitric acid O
Chromium (Cr (NO3)3·9H2O it) is dissolved into solution 1, stirs 1h at room temperature, obtain stable solution 2.
(3) it weighs 0.7gPVP to be added in solution 2, stirs 3h, obtain uniform precursor solution.
(4) electrostatic spinning apparatus for utilizing flat panel collector, is made gallic acid zinc nanofiber, wherein spinning head by precursor solution
It is 15cm, feeding speed 0.15-0.2mL/h, spinning voltage 8-10kV with receiving at a distance from substrate.
(5) the gallic acid zinc nanofiber of collection is dried in an oven.
(6) by step (5), treated that strontium titanates nanofiber is put into tube furnace, and 800 are warming up to certain heating rate
DEG C, 6 hours after annealings are kept the temperature, gallic acid zinc nanofiber is formed.
2. according to the method described in claim 1, it is characterized in that, in the step 1, mixing speed 300-500rpm.
3. according to the method described in claim 1, it is characterized in that, the room temperature is 20~30 DEG C.
4. according to the method described in claim 1, it is characterized in that, drying temperature is preferably 37 DEG C in the step 5.
5. according to the method described in claim 1, it is characterized in that, heating rate is 10 DEG C/min in the step 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810394392.2A CN108517583B (en) | 2018-04-27 | 2018-04-27 | Preparation method of zinc gallate nanofiber material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810394392.2A CN108517583B (en) | 2018-04-27 | 2018-04-27 | Preparation method of zinc gallate nanofiber material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108517583A true CN108517583A (en) | 2018-09-11 |
| CN108517583B CN108517583B (en) | 2020-08-14 |
Family
ID=63429483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810394392.2A Active CN108517583B (en) | 2018-04-27 | 2018-04-27 | Preparation method of zinc gallate nanofiber material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108517583B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345189A (en) * | 2010-08-05 | 2012-02-08 | 同济大学 | Method for preparing porous magnetic and catalytic double-functional one-dimensional composite material |
| CN102650083A (en) * | 2012-05-29 | 2012-08-29 | 上海大学 | Preparation method of high length-diameter-ratio Cadmium Indium 204 (CdIn204) nano fiber material |
| CN105154074A (en) * | 2015-10-10 | 2015-12-16 | 惠州学院 | Chromium-doped red fluorescent powder and preparation method thereof |
| CN106433627A (en) * | 2016-09-13 | 2017-02-22 | 山东大学 | Cr<3+>-doped zinc gallate near-infrared long-afterglow luminescent nanoparticles and preparation method |
| CN107164839A (en) * | 2017-07-18 | 2017-09-15 | 吉林大学 | Formaldehyde sensitive material CdGa2O4 with hypersensitivity and selectivity and preparation method thereof |
-
2018
- 2018-04-27 CN CN201810394392.2A patent/CN108517583B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345189A (en) * | 2010-08-05 | 2012-02-08 | 同济大学 | Method for preparing porous magnetic and catalytic double-functional one-dimensional composite material |
| CN102650083A (en) * | 2012-05-29 | 2012-08-29 | 上海大学 | Preparation method of high length-diameter-ratio Cadmium Indium 204 (CdIn204) nano fiber material |
| CN105154074A (en) * | 2015-10-10 | 2015-12-16 | 惠州学院 | Chromium-doped red fluorescent powder and preparation method thereof |
| CN106433627A (en) * | 2016-09-13 | 2017-02-22 | 山东大学 | Cr<3+>-doped zinc gallate near-infrared long-afterglow luminescent nanoparticles and preparation method |
| CN107164839A (en) * | 2017-07-18 | 2017-09-15 | 吉林大学 | Formaldehyde sensitive material CdGa2O4 with hypersensitivity and selectivity and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LILI WANG ET AL: ""Preparation and luminescence properties of Mn2+-doped ZnGa2O4nanofibersvia electrospinning process"，Lili Wang et al，《Materials Research Bulletin》，第1978–1983页", 《MATERIALS RESEARCH BULLETIN》 * |
| MEGERSA K. HUSSEN ET AL: "Effect of citric acid on material properties of ZnGa2O4：Cr3+ nanopowder prepared by sol–gel method", 《APPLIED PHYSICS A》 * |
| 丁彬等: "《静电纺丝与纳米纤维》", 31 March 2011, 中国纺织出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108517583B (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108138367B (en) | Nanofiber-nanowire composite and method for producing the same | |
| CN104532393B (en) | Anisotropic conductive magneto-optic three function trichroism flag form nano-band array and preparation method thereof | |
| Cena et al. | BSCCO superconductor micro/nanofibers produced by solution blow-spinning technique | |
| CN106466599B (en) | A kind of preparation method of the tungsten trioxide nano fiber of core-shell structure | |
| CN104532394A (en) | Janus nano-belt array with three functions of anisotropy, conductivity and magneto-optic and preparation method thereof | |
| CN106835356B (en) | A method of preparing cobalt protoxide hollow nano fiber | |
| CN106400202A (en) | A method of preparing copper sulphide nanometer fibers | |
| CN104629761A (en) | Calcium titanate up-conversion luminescence nanoparticle and preparation method thereof | |
| CN104528663B (en) | A kind of preparation method of bismuth selenide micron film | |
| CN106391129B (en) | Luminous four two layers of nano-fiber composite films of function of photocatalysis of electromagnetism and preparation method thereof | |
| CN107881593B (en) | Double-anisotropic conductive green fluorescent Janus structure film and preparation method thereof | |
| CN109252290A (en) | Magneto-optic anisotropic conductive special construction Janus nano-band array film | |
| CN108374209A (en) | Three function Janus nanofiber array films of anisotropic conductive magneto-optic | |
| CN108517583A (en) | A kind of preparation method of gallic acid zinc nano-fiber material | |
| CN107794596A (en) | Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof | |
| CN106835366B (en) | A kind of preparation method of cobalt nitride hollow nano fiber | |
| CN108360077A (en) | Three function special construction Janus nanofibers of photoelectromagnetic and preparation method thereof | |
| CN106835355B (en) | A kind of preparation method of calcium carbonate nano fiber | |
| CN109266327A (en) | Double anisotropic conductive flexible compound films of magnetic green fluorescence and preparation method thereof | |
| CN102181289A (en) | Preparation method of orange red fluorescent nano-fiber membrane, namely SrMoO4: Sm3 plus | |
| CN109537164A (en) | Three function sandwich structure composite membrane of anisotropic conductive magneto-optic and preparation method thereof | |
| Mani et al. | Synthesis and photoluminescence studies of one dimensional Sm2MoO6 nanofibers derived from electrospinning process | |
| CN105002597B (en) | ZnO meso-porous nano fibers | |
| CN107604497A (en) | Magneto-optic double-function nano-fibre yams and preparation method thereof | |
| CN109943915B (en) | Preparation method and application of ytterbium and thulium double-doped blue luminescent pyrochlore phase nanofiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |