CN107053649A - Micro-nano composite multi-layer structured polymeric films and preparation method thereof - Google Patents
Micro-nano composite multi-layer structured polymeric films and preparation method thereof Download PDFInfo
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- CN107053649A CN107053649A CN201611249132.3A CN201611249132A CN107053649A CN 107053649 A CN107053649 A CN 107053649A CN 201611249132 A CN201611249132 A CN 201611249132A CN 107053649 A CN107053649 A CN 107053649A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
Abstract
The present invention proposes a kind of micro-nano composite multi-layer structured polymeric films and preparation method thereof, solves that spinning film surface in the prior art is smooth, be unfavorable for cell adhesion and bioactie agent activation the problems such as.The present invention is carried out in the following manner：(1) Bionic Design is utilized, microscale structures are built on master mold；(2) spinning, polymer spinning processing film is pressed on matrix in low-grade fever, (3) hot pressing：Low-grade fever is set to press the matrix squeeze polymer spinning film that deforms to be deformed according to microscale structures shape；(4) it is stripped, then presses matrix and master mold to depart from low-grade fever.The present invention had both maintained the high porosity of simple spinning support, and the active designs and formed precision of the preferable micro-structural for realizing rack surface are controllable, and good forming effect is high in machining efficiency, and yields is high, cell fast growth on hot-pressed material.
Description
Technical field
The present invention relates to the technical field of polymers function film preparation, more specifically to one kind with micron and
The preparation method of the composite multi-layer structured polymeric films of nanoscale, prepared film can be realized super-hydrophobic, super hydrophilic
Characteristic, may be used on the fields such as super-drainage structure, bioengineered tissue support.
Background technology
Histoorgan transplanting is the maximally effective means for the treatment of various Chronic organ's lesions, but the plaque of donor is weary makes always
About histoorgan transplanting.Organizational project provides possibility in vitro culture biological tissue organ, and it is expected to recover tissue
The more biochemical functions of organ.Electrostatic spinning is as a kind of the most frequently used method for obtaining tissue engineering bracket, with simply having
Effect, the advantages of facilitating economic, obtained fiber has continuous length, porous, the characteristic such as ultrafine diameter and high-specific surface area.But it is same
When limited by technique, the spinning film surface being typically prepared is smooth, is unfavorable for the adhesion of cell and the activation of bioactie agent.
Therefore, how to manufacture high specific surface area and suitable surface physicochemical property is in favor of cell adherence, propagation and differentiation and negative
Carrying the biogenic signaling molecules such as growth factor turns into the major issue that tissue engineering bracket is manufactured.
The content of the invention
The present invention proposes a kind of micro-nano composite multi-layer structured polymeric films and preparation method thereof, solves prior art
Middle spinning film surface is smooth, the problems such as being unfavorable for adhesion and the bioactie agent load of cell.
The preparation method of the micro-nano composite multi-layer structured polymeric films of the present invention, is carried out in the following manner：
(1) Bionic Design is utilized, microscale structures are built on master mold；
(2) spinning, low-grade fever pressure matrix is placed on the downside of spinning syringe needle and receives spinning fibre, to be received to finish, spinning film
Together taken out together with low-grade fever pressure matrix, now polymer spinning film is machined on low-grade fever pressure matrix,
(3) hot pressing：Surface with polymer spinning film is close on the microscale structures of master mold, regulation temperature and
Load, makes temperature higher than the glass transition temperature of polymer, less than glutinous circulation temperature, makes low-grade fever press matrix to deform crowded
Compression polymer spinning film deforms according to microscale structures shape；
(4) it is stripped, is pressing matrix and master mold to depart from low-grade fever.
The thickness of polymer spinning film is 1.5-3 times of microscale structures thickness in step (2).
In the step (2) spinning material and low-grade fever pressure substrate material can select PP, PS, PE, PMMA, PC, PLLA,
At least one of PDLA, PVA, PCL, PEG, PEO, PBS or TPU.
The spin processes are melt spinning process, solution spinning, melt spinning method, method of electrostatic spinning or rotary disc spinning process.
Polymer spinning film manufacturing process is as follows：PLA and polyethylene glycol are dissolved in dichloromethane and dimethyl formyl
In amine mixed solution, 12h is stirred in 40 DEG C of thermostat water baths, the wherein mass ratio of PLA and polyethylene glycol is 95:5, two
The volume ratio 7 of chloromethanes and dimethyl formamide solution:3；Then, mixed solution is added in syringe, utilizes electrostatic spinning
Nano-scale fiber film is prepared in machine spinning.
Spinning technique is：Positive voltage 10kv, syringe needle internal diameter 0.9mm, are received apart from 20cm.
Micro- hot pressing parameterses are：65 DEG C of hot pressing temperature, pressure head loading velocity 0.01mm/s, packing pressure 80N, dwell time
300s。
The method of the present invention carries out secondary operation to spinning film, because spinning film has possessed nanostructured, passes through low-grade fever
Pressure technology can build the tissue engineering bracket with micro-nano composite multi-layer structure, both maintain the high hole of simple spinning support
Gap rate, but the active designs and formed precision of the preferable micro-structural for realizing rack surface are controllable, good forming effect, processing effect
Rate is high, and yields is high, cell fast growth on hot-pressed material.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is micro-nano compound structure film preparation principle figure.
Fig. 2 is original nano thin-film shape appearance figure after spinning.
Fig. 3 is the nano thin-film 2D patterns with grating microstructure after hot pressing.
Nano thin-film 3D shape appearance figures after Fig. 4 low-grade fever pressures.
Fig. 5 is Fig. 4 magnified partial view.
Fig. 6 is that HUVECs passes through 1 day, 2 days, the survival ability comparison diagram after culture in 3 days.
Fig. 7 micro structure array silicon mould figures.
Fig. 8 is the SEM pictures of micro-nano laminated film.
Fig. 9 is partial enlarged drawing in Fig. 8.
Figure 10 micro-nano composite polymer films.
Figure 11 is film surface contact angle schematic diagram.
Figure 12 is HUVECs growing state comparison diagrams.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not paid
Embodiment, belongs to the scope of protection of the invention.
As shown in figure 1, a kind of preparation method of micro-nano composite multi-layer structured polymeric films, is to enter in the following manner
Capable：
(1) Bionic Design is utilized, microscale structures 5 are built on master mold 4；
(2) spinning, low-grade fever pressure matrix 2 is placed on the downside of spinning syringe needle and receives spinning fibre, to be received to finish, spinning film
Together taken out together with low-grade fever pressure matrix 2, now polymer spinning film 3 is machined on low-grade fever pressure matrix 2,
(3) hot pressing：Surface with polymer spinning film 3 is close on the microscale structures 5 of master mold 4, regulation temperature
Degree and load, make temperature higher than the glass transition temperature of polymer, less than glutinous circulation temperature, make low-grade fever press matrix 2 to occur
Deformable squeeze polymer spinning film 3 deforms according to the shape of microscale structures 5；
(4) it is stripped, is pressing matrix 2 and master mold 4 to depart from low-grade fever.
It is preferred that, the thickness of polymer spinning film 3 is 1.5-3 times of the thickness of microscale structures 5 in step (2).
It is preferred that, the material of spinning material and low-grade fever pressure substrate 2 can select PP (polypropylene), PS and (gather in the step (2)
Styrene), PE (polyethylene), PMMA (polymethyl methacrylate), PC (makrolon), PLLA (PLA), PDLA (dextrorotation
PLA), PVA (polyvinyl alcohol), PCL (polycaprolactone), PEG (polyethylene glycol), PEO (polyethylene glycol oxide), PBS (polybutadienes
At least one of sour butanediol) or TPU (Polyurethane).
The spin processes are melt spinning process, solution spinning, melt spinning method, method of electrostatic spinning or rotary disc spinning process.
The invention discloses low-grade fever pressure secondary operation is carried out using the polymer spinning film to nanoscale, possessed
The thin polymer film of micro-nano composite multi-layer structure.It is main in this preparation method to be higher than glass in temperature using thermoplastic polymer
Glass transition temperature Tg, and when less than glutinous circulation temperature, polymer is in elastomeric state, modulus of elasticity is low, in this temperature
Polymer spinning film is folded up between low-grade fever compression mould and polymer matrix film, film occurs by low-grade fever compression polymer substrate
Deformation extruding and mould structure control, copying surface goes out the micro-structural corresponding with mould, simultaneously because processing temperature is low
In spinning polymer melting temperature, film remains to retain the nanostructured of spinning.This method is simple to operate, efficiency high, product
Accuracy of repetition is high, can prepare the thin polymer film with micro-nano composite multi-layer structure.It can apply to three-dimensional cell training
Support, organizational project, the field such as super hydrophobic surface.
Illustrate the preparation method of the present invention with reference to specific embodiment.
1. master mold is molded：According to organization bracket surface micro-structure needs, Bionic Design is carried out, micro- chi is built on master mold 4
Very little structure 5；
2. suitable low-grade fever pressure matrix 2 is placed on the downside of spinning syringe needle and receives spinning fibre, to be received to finish, spinning film
Together taken out together with low-grade fever pressure matrix 2, now polymer spinning film 3 is machined on low-grade fever pressure matrix 2, and film surface is put down
Whole, thickness is uniform, generally 1.5-3 times of the thickness of microscale structures 5.
Wherein：Polymer spinning processing film side's specific method and parameter are as follows：PLA and polyethylene glycol are dissolved in two
In chloromethanes and dimethylformamide mixed solution, the magnetic agitation 12h in 40 DEG C of thermostat water baths, wherein PLA and poly- second
The mass ratio of glycol is 95:5, the volume ratio 7 of dichloromethane and dimethyl formamide solution:3；Then, mixed solution is added to
In syringe, nano-scale fiber film is prepared using electrostatic spinning machine spinning.Wherein, spinning technique is：Positive voltage 10Kv,
Syringe needle internal diameter 0.9mm, is received apart from 20cm；Micro- hot pressing parameterses are：65 DEG C of hot pressing temperature, pressure head loading velocity 0.01mm/
S, packing pressure 80N, dwell time 300s.
3 hot pressing：It is molded that the low-grade fever pressure matrix 2 that surface is covered with into spinning film carries out low-grade fever, wherein with polymer spun
The surface of silk film 3 is close to the microscale structures 5 of master mold 4, adjusts temperature, and load makes low-grade fever press matrix 2 to deform and extrudes poly-
Compound spinning film 3 deforms according to the shape of microscale structures 5.Example：PLA (PLLA) film is together with substrate hot pressing temperature
65 DEG C, loading velocity 0.01mm/s, pressurize 300s after loading force reaches 80N.
4 demouldings, during pressing matrix 2 and master mold 4 to depart from low-grade fever, it is ensured that draft angle it is accurate, it is to avoid polymer
The hot pressing micro-structural of spinning film 3 is deformed.
Illustrate the present invention referring to application example：
(1) human vascular endothelial 3D grows support
First, from biocompatibility, Biodegradable polylactic acids (PLLA) and polyethylene glycol (PEG) material, incite somebody to action
Composite polymer is according to certain ratio (PLLA/PEG=95:5 (9wt%)) it is dissolved in dichloromethane (DCM) and dimethyl
(liquor capacity compares 7 in formamide (DMF) mixed solution:3), the magnetic agitation 12h in 40 DEG C of thermostat water baths.Then, will be poly-
Polymer solution is added in syringe, prepares nano-scale fiber film using electrostatic spinning machine as shown in Fig. 2 spinning technique：
Positive voltage 10Kv, syringe needle internal diameter 0.9mm, are received apart from 20cm.Utilize micro- heat pressing process (65 DEG C of hot pressing temperature, pressure head loading speed
Spend 0.01mm/s, packing pressure 80N, dwell time 300s) by microstructure transfer printing to electrostatic spinning film, as shown in Figure 3.Thus
Obtain be in the minute yardstick of space three-dimensional be electrostatic spinning on grating array, nanoscale micro-nano composite multi-layer structure, such as
Shown in Figure 4 and 5.
The cell used in experiment is Human umbilical vein endothelial cells (HUVECs).Cell culture test main agents and main
Instrument is as follows：The culture mediums of BI 1640, BI serum, PBS solution, trypsase containing EDTA, Collagen type-I, Poly-hema, live
And dead assay, CCK8assay, centrifuge, fluorescence microscope, ELIASA.Material surface processing is carried out first：75% wine
Essence immersion film 2h, PLLA film sample PBS solution is rinsed 3 times, and the dual anti-immersion 2h of PBS+, PBS solution is rinsed 3 times, 50ul/ml
Concentration Collagen type-I capsulating material 2h, PBS flushing 3 times, ultraviolet irradiation 30min, culture medium immersion 2h, finally carries out cell training
Support.Cell is planted in 1cm with 3.20e+04cells quantity2On film；37 DEG C of culture cells.First day and the 4th day thin
Intracellular growth situation as shown in figure 12, finds cell in micro- patterned surfaces well-grown.In Figure 12, (a) first day (b) the 4th day
(c) first day (d) the 4th day, HUVECs growing states (a) (b) triangular array；(c) (d) grating array.
Wherein speed of growth test uses CCK8 kits, has six groups of sample (a) orientation fiber (b) random fibers (c)
50 μm of 100 μm of low-grade fever pressure (d), 200 μm of low-grade fever pressure (e) low-grade fever pressures.Experimental result is as shown in Figure 6：PLLA materials are to cell without poison
Property, it is adapted to cell growth, cell increasing on PLLA by three days quantity, and the speed of growth is more on hot-pressed material for cell
It hurry up, hot-pressed material is more suitable for cell growth.
Super-hydrophobic micro-nano compound structure PC spinning films：Electrostatic spinning be it is a kind of prepare polymer nanocomposite film have efficacious prescriptions
Method, and low-grade fever pressure can be by being heated to deformation temperature silicon template duplicating micro-structural utilized above by polymeric material.We will
Low-grade fever is molded to be combined with electrostatic spinning, prepares and a kind of possesses micro-meter scale but also with nano-material surface feature
Micro-nano composite multi-layer polymer surfaces.Fig. 7 is used silicon template, and low-light grid array characteristic size is 100 microns, spacing
100-200 microns；Micro- cylindrical-array characteristic size is 40,80 microns, 100-200 microns of spacing.Fig. 8 and 9 is to utilize Static Spinning
The SEM pictures of PC nano-fiber films prepared by silk, it can be seen that the random arrangement of nanofiber.PC heat distortion temperatures it
On, after hot pressing, micro structure array copies to PC electrostatic spinning films.Figure 10 is shown on micro-nano laminated film micro-
Pattern under mirror, micro structure array is clear, from Fig. 9 it can be seen that the nanofiber pattern at micro- cylindrical projection position by not by
Destruction.Contact angle test is carried out to the micro-nano laminated film of different templates hot pressing, such as Figure 11 is the contact of the film of optical grating construction
Angle situation, due to the anisotropic of optical grating construction, therefore testing level and the contact angle of vertical direction, (a) electrostatic spinning respectively
Film；(b) micro structure array；(c) micro-nano laminated film；It can be seen that the micro-nano composite multi-layer structure PC films prepared have
Super-hydrophobic characteristic.This micro-nano composite multi-layer architectural feature will be before self-cleaning surface Material Field has application well
Scape.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (8)
1. a kind of preparation method of micro-nano composite multi-layer structured polymeric films, it is characterised in that be to carry out in the following manner
's：
(1) Bionic Design is utilized, microscale structures (5) are built on master mold (4)；
(2) spinning, presses matrix (2) to be placed on the downside of spinning syringe needle low-grade fever and receives spinning fibre, to be received to finish, spinning film connects
Together taken out with low-grade fever pressure matrix (2), now polymer spinning film (3) is machined on low-grade fever pressure matrix (2),
(3) hot pressing：Surface with polymer spinning film (3) is close on the microscale structures of master mold (4) (5), adjusted
Temperature and load, make temperature higher than the glass transition temperature of polymer, less than glutinous circulation temperature, low-grade fever is pressed matrix (2)
The squeeze polymer spinning film (3) that deforms deforms according to microscale structures (5) shape；
(4) it is stripped, is pressing matrix (2) and master mold (4) to depart from low-grade fever.
2. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 1, it is characterised in that：Step
Suddenly the thickness of polymer spinning film (3) is 1.5-3 times of microscale structures (5) thickness in (2).
3. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 1 or 2, its feature exists
In：In the step (2) spinning material and low-grade fever pressure substrate (2) material can select PP, PS, PE, PMMA, PC, PLLA,
At least one of PDLA, PVA, PCL, PEG, PEO, PBS or TPU.
4. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 1 or 2, its feature exists
In：The spin processes are melt spinning process, solution spinning, melt spinning method, method of electrostatic spinning or rotary disc spinning process.
5. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 1, it is characterised in that poly-
Compound spinning film manufacturing process is as follows：PLA and polyethylene glycol are dissolved in dichloromethane and dimethylformamide mixed solution
In, 12h is stirred in 40 DEG C of thermostat water baths, the wherein mass ratio of PLA and polyethylene glycol is 95:5, dichloromethane and two
The volume ratio 7 of NMF solution:3；
Then, mixed solution is added in syringe, nano-scale fiber film is prepared using electrostatic spinning machine spinning.
6. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 5, it is characterised in that spin
Silk technique be：Positive voltage 10kv, syringe needle internal diameter 0.9mm, are received apart from 20cm.
7. the preparation method of micro-nano composite multi-layer structured polymeric films according to claim 5, it is characterised in that micro-
Hot pressing parameterses are：65 DEG C of hot pressing temperature, pressure head loading velocity 0.01mm/s, packing pressure 80N, dwell time 300s.
8. a kind of micro-nano composite multi-layer structured polymeric films prepared such as claim 1~7 methods described.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525013A (en) * | 2018-03-23 | 2018-09-14 | 南通大学 | A kind of preparation method of tissue-engineering graft constructed of the surface with micron-nano topological geometry |
| CN109961952A (en) * | 2019-03-27 | 2019-07-02 | 哈尔滨理工大学 | A kind of multiple layer polymer base composite energy-storage material of heterojunction structure and preparation method thereof |
| CN111821510A (en) * | 2019-04-19 | 2020-10-27 | 郑州大学 | Polymer tissue engineering scaffold microporous material containing nano-filaments and preparation method thereof |
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| CN204608227U (en) * | 2015-05-14 | 2015-09-02 | 四川农业大学 | A kind of patternable, high efficiency electrostatic spinning apparatus |
| JP5937868B2 (en) * | 2012-03-30 | 2016-06-22 | グンゼ株式会社 | Method for producing ultrafine fiber nonwoven fabric and electrospinning apparatus |
| CN106172734A (en) * | 2016-07-27 | 2016-12-07 | 四川农业大学 | A kind of strawberry preservation composite package film and preparation method thereof |
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| JP5937868B2 (en) * | 2012-03-30 | 2016-06-22 | グンゼ株式会社 | Method for producing ultrafine fiber nonwoven fabric and electrospinning apparatus |
| CN102965849A (en) * | 2012-11-22 | 2013-03-13 | 天津大学 | Method for preparing medical barrier membrane by electrostatic spinning |
| CN204608227U (en) * | 2015-05-14 | 2015-09-02 | 四川农业大学 | A kind of patternable, high efficiency electrostatic spinning apparatus |
| CN106172734A (en) * | 2016-07-27 | 2016-12-07 | 四川农业大学 | A kind of strawberry preservation composite package film and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525013A (en) * | 2018-03-23 | 2018-09-14 | 南通大学 | A kind of preparation method of tissue-engineering graft constructed of the surface with micron-nano topological geometry |
| CN109961952A (en) * | 2019-03-27 | 2019-07-02 | 哈尔滨理工大学 | A kind of multiple layer polymer base composite energy-storage material of heterojunction structure and preparation method thereof |
| CN111821510A (en) * | 2019-04-19 | 2020-10-27 | 郑州大学 | Polymer tissue engineering scaffold microporous material containing nano-filaments and preparation method thereof |
| CN111821510B (en) * | 2019-04-19 | 2023-09-12 | 郑州大学 | Polymer tissue engineering scaffold microporous material containing nano wires and preparation method thereof |
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| CN107053649B (en) | 2019-04-23 |
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