CN104844833B - Red light conversion film and preparation method and application thereof - Google Patents
Red light conversion film and preparation method and application thereof Download PDFInfo
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- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a red light conversion film and a preparation method and an application thereof. The red light conversion film comprises a light conversion agent and a carrier; a red fluorescent powder is selected and used as the light conversion agent, and cellulose is selected and used as the carrier; the cellulose is a most abundant natural polymer on the earth and has the advantages of being safe, non-toxic and renewable, and a synthetic material of the cellulose not only has excellent mechanical properties but also is biodegradable. The red light conversion film is an important change to a conventional agricultural polymer material thin film; the natural polymer and the light conversion agent are combined, conventional renewable green resources are fully utilized, environmental problems brought by synthetic polymer is avoided, and optical properties are increased based on the traditional thin film. The light conversion film has high-efficiency stimulation at the wavelength of 200-600 nm, and can convert ultraviolet light and a part of visible light into red light useful for plant growth so as to improve the utilization rate of light energy; and the light conversion film can be used as agricultural greenhouse films and plastic films and is applied in crop cultivation, seedling growing and other aspects.
Description
Technical field
Turn light technical field the invention belongs to agricultural, and in particular to a kind of red conversion film and preparation method and application.
Background technology
With the continuous propulsion of building a knowledge-driven society, scientific and technological information and economic globalization, the strategy of sustainable development seems outstanding
It is important and protrusion.However, being faced with scarcity of resources and the hang-up of environmental pollution two at present, how this is caused using existing green
Colour circle protects resource has far reaching significance.Cellulose is the most abundant natural polymer of reserves on the earth, be nature it is inexhaustible,
Nexhaustible renewable resource.With synthesize macromolecule compared with, cellulose also have fully biodegradable, nontoxic pollution-free,
The advantages such as easily modified, good biocompatibility, it is considered to be the primary raw material of future world derived energy chemical.
Sunshine is that plant carries out photosynthetic energy source.But plant is to the demand of luminous energy, most important of which
It is exactly light quality, not only influences the photosynthetic efficiency of crop, the nutritional ingredient of crop can also be regulated and controled.In sunshine feux rouges (600~
Photosynthesis 700nm) to plant is mostly important, next to that blue light (400~500nm)；Ultraviolet light (200~400nm) is then easy
In promoting, limb is aging and germ reproduction, has harmful effect to the growth of plant；Remaining a part of light is then mainly converted into carrying
The heat energy of high-temperature.
Light conversion agent is that ultraviolet useless to photosynthesis of plant in sunshine, purple light and green glow are converted into plant life
Feux rouges and blue light needed for long.For red light conversion agent, mainly based on Eu doped substrates and Mn doped substrates, for example
Sr2Si5N8:Eu2+、CaAl12O19:Mn4+、3.5MgO·0.05MgF2·GeO2:Mn4+、Y2O3:Eu3+、Y2O2S:Eu3+Deng 200
Exist in~600nm wave-length coverages and efficiently excite, the feux rouges that plant can absorb can be converted into.
Agricultural film is mainly and is processed by polyethylene etc. at present, and polyethylene synthesizes macromolecule as one kind, its
Raw material is fairly limited, additionally, polyethylene is difficult degraded, generally requires by 80 years, and even going up a century just has part to be decomposed.
Therefore, the use of polyethylene film, is not only the significant challenge to the existing energy, even more brings grave danger to environment.And
And, the effect of ordinary agricultural membrane is only limited to improve surface temperature, it is ensured that the humidity of soil, and light effect is not turned.
The content of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the invention is to provide a kind of red conversion film.
Preparation method another object of the present invention is to provide above-mentioned red conversion film.Conversion film work prepared by the method
Skill process is simple, does not chemically react, pollution-free, excellent performance, it is easy to industrialized production.
It is still another object of the present invention to provide the application of above-mentioned red conversion film.
The purpose of the present invention is achieved through the following technical solutions：A kind of red conversion film, including light conversion agent and carrier.
Described light conversion agent selects red fluorescence powder, preferably Sr2Si5N8:Eu2+、CaAl12O19:Mn4+、3.5MgO·
0.05MgF2·GeO2:Mn4+、Y2O3:Eu3+、Ca2Si5N8:Eu2+、CaAlSiN3:Eu2+、Gd2Mo3O9:Eu3+、YVO4:Eu3+With
Y2O2S:Eu3+At least one in.
Described carrier is cellulosic polymer, biodegradable, is a class green compounds.
The excitation wavelength of described red conversion film is preferably 200~600nm；
The launch wavelength of described red conversion film is preferably 500~800nm；
Described red conversion film can absorb ultraviolet light and a part of visible ray, be converted into the feux rouges that can be utilized.
A kind of preparation method of red conversion film, comprises the following steps：
(1) cellulose dissolution：Cellulose is added in dissolution system, strong agitation obtains cellulose solution；
(2) recombination process：Light conversion agent is added into the cellulose solution of step (1), lasting stirring makes light conversion agent in fibre
It is dispersed in the plain solution of dimension, after sloughing bubble, obtain homogeneous composite solution；
(3) film-forming：The composite solution that step (2) is obtained casting film-forming on a glass, solidifies by coagulator
Shaping, washs drying, obtains final product red conversion film.
Dissolution system described in step (1) is preferably NaOH/ urea combination solution and N-methylmorpholine-N- oxides
It is a kind of in the aqueous solution；
Described NaOH/ urea combination solutions are preferably the combination solution of 7wt%NaOH/12wt% urea；
Water content in described N-methylmorpholine-N- oxide water solutions is preferably 13%~17%；
The concentration of cellulose is preferably 3%~5.2% in cellulose solution described in step (1).
Cellulose dissolution described in step (1) by destroying cellulosic molecule between hydrogen bond action carry out, belong to non-
Derivatization process.
Light conversion agent in step (2) selects red fluorescence powder, preferably Sr2Si5N8:Eu2+、CaAl12O19:Mn4+、
3.5MgO·0.05MgF2·GeO2:Mn4+、Y2O3:Eu3+、Ca2Si5N8:Eu2+、CaAlSiN3:Eu2+、Gd2Mo3O9:Eu3+、
YVO4:Eu3+And Y2O2S:Eu3+At least one in.
Light conversion agent is preferably 1 with the mass ratio of cellulose in composite solution described in step (2)：(13~80).
Recombination process described in step (2) is a physical process, and light conversion agent can be made with individual event or multinomial any apolegamy
With.
Coagulator described in step (3) is preferably 5wt%H2SO4Solution；
Described red conversion film can be applied to the aspects such as crop-planting and nursery as agriculture canopy film and mulch film.
The present invention has the following advantages and effect relative to prior art：
(1) red conversion film of the invention selects cellulose as carrier, rich reserves, sustainable production.Cellulose is
The most abundant natural polymer of reserves on the earth, the annual cellulose produced by photosynthesis, up to more than 100,000,000,000 tons, is certainly
Inexhaustible, nexhaustible renewable resource in right boundary.
(2) red conversion film of the invention is biodegradable, belongs to Green Product.Cellulose is that a class is rich in carbon source
Compound, can be degraded by the bacterium in soil or sludge, fungi and actinomyces etc..Also, in the process, will not produce
Poison, harmful substance, meet the requirement that mass production is used.
(3) present invention is the material alterations to existing agricultural macromolecule material film, as a kind of red conversion film, by day
Right macromolecule combines with light conversion agent, both taken full advantage of existing renewable green resource, it is to avoid synthesis macromolecule institute
The environmental problem brought, and increased optical property on traditional Membranous Foundations.
(4) red conversion film of the invention has excellent optical property.It is presented with 3 points：Conversion film Stability Analysis of Structures, turns
Photo etching forms strong interaction with cellulose, with good water resistance；Conversion film has the optical property of stabilization, selects
Light conversion agent be Crystalline Compound, stable chemical nature；Conversion film exists between 200~600nm and efficiently excites, can be by
Ultraviolet light and a part of visible ray are converted into the feux rouges useful to plant growth, improve the efficiency of light energy utilization.
Brief description of the drawings
Fig. 1 is light conversion agent Sr2Si5N8:Eu2+Excite, launching light spectrogram.
Fig. 2 is light conversion agent Sr2Si5N8:Eu2+Scanning electron microscope (SEM) photograph.
Fig. 3 is the exciting of red conversion film obtained in embodiment 3, launching light spectrogram.
Fig. 4 is the exciting of red conversion film obtained in embodiment 4, launching light spectrogram.
Fig. 5 is the exciting of red conversion film obtained in embodiment 5, launching light spectrogram.
Fig. 6 is the exciting of red conversion film obtained in embodiment 6, launching light spectrogram.
Fig. 7 is the scanning electron microscope (SEM) photograph of red conversion film obtained in embodiment 7.
Fig. 8 is that red conversion film obtained in embodiment 7 turns light effect figure.
Fig. 9 is launching light spectrogram of the red conversion film in the case where different wave length is excited obtained in embodiment 7.
Figure 10 is exciting light spectrogram (λ em=614nm) of the different quality obtained in embodiment 8 than conversion film.
Figure 11 is launching light spectrogram (λ ex=256nm) of the different quality obtained in embodiment 8 than conversion film.
Figure 12 is mechanical property figure of the different quality obtained in embodiment 8 than conversion film.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
The preparation method of red conversion film can be divided into cellulose dissolution, recombination process and film-forming three phases：
By combination solutions of the 100g containing 7wt%NaOH/12wt% urea, -12 DEG C~-13 DEG C are cooled in advance, added certain
The cotton oar (being purchased from Hubei Chemical-Fiber Group Co., Ltd., DP=580) of amount, quick stirring obtains 4wt% cellulose solutions.Then
Take the Sr of 0.10g2Si5N8:Eu2+(light conversion agent Sr2Si5N8:Eu2+Excite, emission spectrum, see Fig. 1；Light conversion agent Sr2Si5N8:Eu2 +ESEM, see Fig. 2) be added in above-mentioned solution, continue to stir 30min, make its dispersed, it is de- through supercentrifuge
Bubble is removed, (light conversion agent and the mass ratio of cellulose are 1 in composite solution to obtain composite solution:40).By composite solution in glass
On plate after casting film-forming, 5wt%H is immersed in immediately2SO4Curing molding in solution, takes out washing after 2min, be laid in glass plate
Upper natural drying, obtains final product red conversion film.
Embodiment 2
By 100g methyhnorpholine-N-oxides containing the 50wt%N- aqueous solution, the vacuum distillation at 85 DEG C, until water content drop
Untill for 13.3wt% or so, 3g cotton pulps are subsequently adding, stirring a period of time, prepared transparent, filbert cellulose/NMMO is molten
Liquid (wherein, the final concentration of 5.2wt% of cellulose).It is subsequently added into the Sr of 0.2g2Si5N8:Eu2+, 30min is persistently stirred, make it
It is dispersed in cellulose mixed solution, bubble is sloughed, obtain the composite solution (matter of light conversion agent and cellulose in composite solution
Amount ratio is 1:15).By composite solution after casting film-forming on hot glass sheet, make its curing molding, through distilling water washing, be laid in
Spontaneously dried on glass plate, obtain final product red conversion film.
Embodiment 3
By combination solutions of the 100g containing 7wt%NaOH/12wt% urea, -12 DEG C~-13 DEG C are cooled in advance, added certain
The cotton oar of amount, quick stirring, obtains 4wt% cellulose solutions.It is subsequently added into the CaAl of 0.20g12O19:Mn4+, continue to stir
30min, makes it dispersed in the solution of cellulose, and bubble is sloughed by supercentrifuge, obtains composite solution (composite solution
Middle light conversion agent is 1 with the mass ratio of cellulose:20).After by composite solution on a glass casting film-forming, it is immersed in immediately
5wt%H2SO4Curing molding in solution, takes out washing after 2min, tiling is spontaneously dried on a glass, obtains final product red conversion film.
The exciting of gained conversion film, launching light spectrogram are as shown in Figure 3 (with the XRF of day (China) scientific instrument Co., Ltd of U.S.
F-7000 is tested).
Embodiment 4
By combination solutions of the 100g containing 7wt%NaOH/12wt% urea, -12 DEG C~-13 DEG C are cooled in advance, added certain
The cotton oar of amount, obtains 4wt% cellulose solutions after stirring.Take the 3.5MgO0.05MgF of 0.1g2·GeO2:Mn4+, it is added to
In above-mentioned solution, continue to stir 30min, make it dispersed in the solution of cellulose, bubble is sloughed through supercentrifuge, obtain
To composite solution, (light conversion agent and the mass ratio of cellulose are 1 in composite solution:40).Composite solution is cast on a glass
Film, is immersed in 5wt%H immediately2SO4Curing molding in solution, takes out washing after 2min, then tile and do naturally on a glass
It is dry, obtain final product red conversion film.The exciting of gained conversion film, launching light spectrogram (have with beautiful (China) scientific instrument in day as shown in Figure 4
The XRF F-7000 of limit company is tested).
Embodiment 5
By combination solutions of the 100g containing 7wt%NaOH/12wt% urea, -12 DEG C~-13 DEG C are cooled in advance, added certain
The cotton oar of amount, quick stirring, obtains 4wt% cellulose solutions.Add the Y of 0.30g2O3:Eu3+, 30min is persistently stirred, make
It is dispersed in the solution of cellulose, and bubble is sloughed through supercentrifuge, obtains composite solution (light conversion agent in composite solution
It is 1 with the mass ratio of cellulose:13).After by composite solution on a glass casting film-forming, 5wt%H is immersed in immediately2SO4It is molten
Curing molding in liquid, takes out washing after 2min, then tile and spontaneously dry on a glass, obtains final product red conversion film.Gained turns
The exciting of light film, launching light spectrogram are as shown in Figure 5 (with the XRF F-7000 of day (China) scientific instrument Co., Ltd of U.S.
Tested).
Embodiment 6
By combination solutions of the 100g containing 7wt%NaOH/12wt% urea, -12 DEG C~-13 DEG C are cooled in advance, added certain
The cotton oar of amount, quick stirring, obtains 4wt% cellulose solutions.It is subsequently added into the Y of 0.150g2O2S:Eu3+, lasting stirring
30min, makes it dispersed in the solution of cellulose, and bubble is sloughed through supercentrifuge, obtains composite solution (composite solution
Middle light conversion agent is 1 with the mass ratio of cellulose:27).After by composite solution on a glass casting film-forming, it is immersed in immediately
5wt%H2SO4Curing molding in solution, takes out washing after 2min, then tile and spontaneously dry on a glass, obtains final product red turning
Light film.The exciting of gained conversion film, launching light spectrogram are as shown in Figure 6 (with the fluorescence of day (China) scientific instrument Co., Ltd of U.S.
Spectrometer F-7000 is tested).
Embodiment 7
The preparation method reference implementation example 1 of red conversion film, with being a difference in that for embodiment 1：Light conversion agent in conversion film
It is 5% with the mass ratio of cellulose；The ESEM of the conversion film is as shown in Figure 7.To turning for the red conversion film of above-mentioned preparation
Light effect is tested, as a result as shown in Figure 8.Wherein, Fig. 8 left figures are the abosrption spectrograms of conversion film (with Jing Dao companies of Japan
Ultraviolet-uisible spectrophotometer UV-2550 tested)；Fig. 8 right figures are that the launching light spectrogram of conversion film is (beautiful with day
The XRF F-7000 of (China) scientific instrument Co., Ltd is tested).Different light conversion agents turns light effect not
Together, all it is that can absorb ultraviolet light and a part of visible ray but as a kind of red conversion film, then launches feux rouges
(500~800nm).
Emission spectrum of the above-mentioned preparation red conversion film in the case where different wave length is excited is tested；Tester：Fluorescence
Spectrometer F-7000 (day (China) scientific instrument Co., Ltd of U.S.).Result is as shown in Figure 9.By selecting different excitation waves
It is long, the wavelength spectra of conversion film can be obtained.Different light conversion agents, launching light spectrogram is different, but the peak value of emission spectrum
Necessarily, and all between 500~800nm.
Embodiment 8
The preparation method reference implementation example 1 of red conversion film, with being a difference in that for embodiment 1：Light conversion agent in conversion film
0,1.25%, 2.5%, 3.75%, 5% is respectively with the mass ratio of cellulose.In the launch wavelength (λ em=614nm) of 614nm
Under, to above-mentioned different quality than the excitation spectrum of conversion film test；Tester：(it is beautiful for XRF F-7000
(China) scientific instrument Co., Ltd).Result is as shown in Figure 10.Different quality is than the red conversion film that obtains, its excitation spectrum
Difference, but all it is to increase with the mass ratio increase of light conversion agent and cellulose.
Under the excitation wavelength (λ ex=256nm) of 256nm, to above-mentioned different quality than the emission spectrum of conversion film enter
Row test；Tester：XRF F-7000 (day (China) scientific instrument Co., Ltd of U.S.).Result is as shown in figure 11.
Different quality is than the red conversion film that obtains, and its emission spectrum is different, but is all the mass ratio with light conversion agent and cellulose
Increase and increase.
Using spectrophotometer test different quality than conversion film light transmittance；The instrument of test：UV, visible light light splitting
Photometer UV-2550 (Japanese Jing Dao companies).Reference is made with air, conversion film thickness is 24 μm, the light transmittance at 800nm,
Result such as following table：
| Conversion film mass ratio (%) | 1.25 | 2.5 | 3.75 | 5 |
| Light transmittance (%) | 66 | 40 | 32 | 18 |
To the different quality of above-mentioned preparation than conversion film carry out Mechanics Performance Testing；The instrument of test：The omnipotent survey of material
Test-run a machine UTM4204 (thinks carefully testing of materials instrument Co., Ltd in Shenzhen).Result is as shown in 12.Method of testing：By material cutting into
The strip of 1.2 × 15cm, the distance controlling of fixture is 10cm, load 200N, and the speed of stretching is 5mm/min.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of preparation method of red conversion film, it is characterised in that：Comprise the following steps：
(1) cellulose dissolution：Cellulose is added in dissolution system, strong agitation obtains cellulose solution；
(2) recombination process：Light conversion agent is added into the cellulose solution of step (1), lasting stirring makes light conversion agent in cellulose
It is dispersed in solution, after sloughing bubble, obtain homogeneous composite solution；
(3) film-forming：The composite solution casting film-forming that step (2) is obtained, by coagulator curing molding, washs drying,
Obtain final product red conversion film；
Described light conversion agent selects red fluorescence powder；Described red fluorescence powder is Sr2Si5N8:Eu2+、CaAl12O19:Mn4+、
3.5MgO·0.05MgF2·GeO2:Mn4+、Y2O3:Eu3+、Ca2Si5N8:Eu2+、CaAlSiN3:Eu2+、Gd2Mo3O9:Eu3+、
YVO4:Eu3+And Y2O2S:Eu3+In at least one；
Dissolution system described in step (1) is in NaOH/ urea combination solution and N-methylmorpholine-N- oxide water solutions
It is a kind of；
Described NaOH/ urea combination solution is the combination solution of 7wt%NaOH/12wt% urea；
Water content in described N-methylmorpholine-N- oxide water solutions is 13%~17%.
2. the preparation method of red conversion film according to claim 1, it is characterised in that：Described red conversion film swash
Hair wavelength is 200~600nm；
The launch wavelength of described red conversion film is 500~800nm.
3. preparation method according to claim 1, it is characterised in that：Fiber in cellulose solution described in step (1)
The concentration of element is 3%~5.2%；
Light conversion agent and the mass ratio of cellulose are 1 in composite solution described in step (2)：(13~80).
4. the red conversion film that prepared by preparation method described in any one of claims 1 to 3 in terms of the crop-planting and nursery on
Application.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510177689.XA CN104844833B (en) | 2015-04-15 | 2015-04-15 | Red light conversion film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510177689.XA CN104844833B (en) | 2015-04-15 | 2015-04-15 | Red light conversion film and preparation method and application thereof |
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| CN105315695B (en) * | 2015-10-29 | 2017-08-18 | 严梅霞 | A kind of agricultural film and its manufacture method |
| CN105482816A (en) * | 2015-11-17 | 2016-04-13 | 佛山安亿纳米材料有限公司 | Nitride red light conversion master batch and preparation method thereof |
| CN105295188A (en) * | 2015-11-17 | 2016-02-03 | 佛山安亿纳米材料有限公司 | Nitride red light conversion film and preparation method thereof |
| CN105385014B (en) * | 2015-12-11 | 2018-06-12 | 华南农业大学 | A kind of light altering film for agriculture and preparation method and application |
| CN109593222B (en) * | 2018-11-05 | 2021-07-09 | 广东工业大学 | Plant light conversion film and preparation method and application thereof |
| CN109638145B (en) * | 2018-11-22 | 2021-03-26 | 华南农业大学 | Red and blue light glass ceramic light conversion assembly, preparation method and plant lamp |
| CN112480479B (en) * | 2020-11-30 | 2022-02-01 | 江南大学 | Preparation method of nanocellulose-based fluorescent film |
| CN113980681A (en) * | 2021-11-25 | 2022-01-28 | 济南鲁新新型建材股份有限公司 | Metal ion doped rare earth phosphate red light conversion agent and preparation method and application thereof |
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