CN111876145A - Light conversion film capable of promoting plant growth and preparation method thereof - Google Patents
Light conversion film capable of promoting plant growth and preparation method thereof Download PDFInfo
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- CN111876145A CN111876145A CN202010630215.7A CN202010630215A CN111876145A CN 111876145 A CN111876145 A CN 111876145A CN 202010630215 A CN202010630215 A CN 202010630215A CN 111876145 A CN111876145 A CN 111876145A
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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Abstract
The invention discloses a light conversion film capable of promoting plant growth and a preparation method thereof, wherein the light conversion film contains a component Y(3‑x)BaxAl(5‑x)SixO12mCE, nCr, 0 ≦ x ≦ 1, m > 0, n > 0, and a polymer resin or glass having a refractive index of 1.4 to 1.65, the garnet phosphor being uniformly dispersed in the polymer resin or glass. The preparation method comprises the following steps of 1) respectively weighing compound raw materials of yttrium, aluminum, barium, silicon, chromium and cerium according to the stoichiometric ratio of each chemical composition of the expression: mixing and grinding to micron level; 2): calcining the raw material powder in a reducing atmosphere for 4-5 hours; obtaining a calcined substance; and step 3: grinding the calcined substance to micron level to obtain fluorescent powder containing Ce and Cr and having a garnet structure, wherein the mass ratio of the fluorescent powder to the polymer resin is 1: 4-1: 1Mixing, and preparing the light conversion film according to the existing film preparation process. The advantages are that: the emission intensity of the fluorescent powder in a red light area is greatly enhanced, the light supplementing capacity for plants is strong, the efficiency is high, and the growth of the plants is promoted.
Description
Technical Field
The invention belongs to the technical field of agricultural light conversion materials, and relates to a light conversion film for plant growth.
Background
The plant needs light to provide energy in the growth and development process, so the light regulation is one of important means for regulating and controlling the plant growth, and the plant growth fluorescent powder is the fluorescent powder for promoting the rapid growth of the plant and shortening the mature period. The absorption of light by plants is mainly carried out by chlorophyll and carotenoids, the absorbed light is light in the blue region (400 nm-500 nm) and red region (600 nm-700 nm), respectively, and the light sensitive pigment absorbs light in the red and deep red region (650 nm-750 nm), respectively corresponding to phototropism, photosynthesis and light morphology. Of these, light in the red region (600 nm to 700 nm) is most important for plant growth, because red light is greatly affected at the flowering and maturity stages of plants. Since light outside this range is less absorbed, the utilization of sunlight during the growth of the plant is low. Therefore, the improvement of the light utilization rate of the plants has important influence on the growth of the plants, and the improvement of the light energy utilization rate of the plants can greatly promote the growth speed of the plants and improve the yield.
At present, most of fluorescent powder for promoting plant growth is used for LED plant lamps for indoor plant cultivation. In order to better promote the growth of economic crops, the LED plant growth lamp mainly adopts high-cost red fluorescent powder. However, LED plant lights have a number of disadvantages: the spectral curve of the LED plant lamp on the market at present has a large difference with the spectral curve absorbed by plant photosynthesis, the energy utilization rate of a light source is low, the price of an LED chip is high, and a large amount of power resources are consumed. Thereby increasing planting costs and wasting resources. Therefore, although the indoor LED plant growth factory can improve the crop yield, the indoor LED plant growth factory is not suitable for cultivating low-economic crops which are just vegetables, fruits and the like required by people in daily life, so that the LED plant growth lamp is difficult to be widely applied.
There is also a method of converting sunlight into red light to promote plant growth, in which plants are covered with an organic red light emitting material such as a vinyl film containing a heterocyclic compound, like a conventional plant vinyl house. However, ultraviolet light is present in sunlight and is harmful to the film, causing the film to yellow and decompose. The material is unstable in the sun and the emitted red light will decay within 3 months. Furthermore, this method of covering the plants with a film does not provide the plants with an intense red light, since half of the red light emitted by the film is emitted outside the plants.
In order to solve the above disadvantages of plant lamps and the instability of the film, we proceed with the following ideas. First, it is important to still utilize sunlight, rather than the expensive LED plant lights. Second, a stable, inexpensive film or plate can effectively convert white light in sunlight to red or deep red light. Third, most of the red or deep red light generated by such films or plates impinges on the plants. Therefore, the idea can be satisfied only by preparing the fluorescent powder into a light conversion film or a flat plate, and better conditions are provided for plant growth. Therefore, it is necessary and significant to design a new light conversion film or plate that is inexpensive and can improve the utilization rate of solar radiation energy by plants.
Disclosure of Invention
The invention aims to provide a solar energy conversion film which is low in cost and capable of improving the utilization rate of light energy, and a preparation method.
The technical scheme of the invention is as follows: a light conversion film for promoting plant growth is in the form of film with thickness of μm and composition Y(3-x)BaxAl(5-x)SixO12mCE, nCr, 0 ≦ x ≦ 1, m > 0, n > 0, and a polymer resin or glass having a refractive index of 1.4 to 1.65, the garnet phosphor being uniformly dispersed in the polymer resin or glass.
The garnet phosphor has a maximum emission peak in the region of 660-700 nm.
The polymer resin is polycarbonate or epoxy resin.
Step 1) according to the expression Y(3-x)BaxAl(5-x)SixO12mCE, nCr, x is less than or equal to 0 and less than or equal to 1, m is more than 0, n is more than 0, and the following raw materials are respectively weighed according to the stoichiometric ratio of each chemical composition:
yttrium compound: using yttrium oxide Y2O3Or yttrium-containing hydroxides or nitrates, carbonates or sulfates or phosphates;
an aluminum compound: using yttrium oxide Al2O3Or aluminium-containing hydroxides or nitrates or sulphates or phosphates;
a barium compound: by using barium carbonate BaCO3Or a barium-containing hydroxide or a barium-containing nitrate or a barium-containing sulfate or a barium-containing phosphate;
silicon compound (b): using silicon dioxide SiO2Or a silicon-containing hydroxide or a silicon-containing nitrate or a silicon-containing carbonate or a silicon-containing sulfate or a silicon-containing phosphate;
a chromium compound: using chromium oxide Cr2O3Or chromium-containing hydroxides or nitrates, carbonates or sulfates or phosphates;
a cerium compound: using cerium oxide CeO2Or a cerium-containing hydroxide or nitrate, a cerium-containing carbonate or a cerium-containing sulfate or a cerium-containing phosphate;
mixing the weighed raw material components together and grinding the mixture to micron level to obtain mixed raw material powder;
step 2): calcining the mixed raw material powder obtained in the step 1) in a reducing atmosphere at the temperature of 1400-1500 ℃ for 4-5 hours; cooling the calcined material to room temperature along with the furnace to obtain a calcined substance;
and step 3: grinding the calcined substance to micron level to obtain fluorescent powder with a garnet structure containing Ce and Cr, mixing the fluorescent powder with polymer resin according to the mass ratio of 1: 4-1: 1, and preparing the light conversion film according to the existing film preparation process (the prepared light conversion film is attached to a plate by a film coating machine).
The reducing atmosphere can adopt the following gases: ammonia NH3Or 5 to 25% by volume of hydrogen H2And 95 to 75% Nitrogen N2The mixed gas is composed of 5-25% of CO and 95-75% of N2The composition of the mixed gas.
It is preferable that: the polymer resin is epoxy A, B glue, epoxy A, B glue is mixed according to the mass ratio of 1:1, the fluorescent powder and the mixed glue are mixed according to the mass ratio of 1: 4-1: 1, then the mixture is stirred for 2.5 minutes in a vacuum defoaming machine, after being uniformly stirred, the mixture is placed in an oven to be dried, and the dried material is attached to a plate, such as a plastic plate, through a film coating machine.
Further, 4wt% of AlF was added3Fluxing agent, AlF3Mixing with the weighed raw materials, and grinding.
The invention has the beneficial effects that: 1. the product has wide excitation spectrum coverage area, can be directly excited by visible light, and does not need to be manufactured into a chip. The emission intensity of the fluorescent powder in a red light area is greatly enhanced, the light supplementing capacity for plants is strong, the efficiency is high, and the growth of the plants is promoted. Can absorb ultraviolet light, thereby avoiding the yellowing and disintegration of the film caused by sunlight.
2. The preparation method adopts high-temperature calcination, and has the advantages of simple preparation method and low cost; the fluorescent powder in the obtained film is uniformly distributed, and the equipment is simple to operate.
Drawings
FIG. 1 is Y obtained in example 12BaAl4SiO12The XRD pattern of the Ce and Cr fluorescent powder 1 is compared with that of a standard card.
FIG. 2 is Y obtained in example 12BaAl4SiO12Excitation and emission spectra of the Ce, Cr phosphor 1.
FIG. 3 is Y obtained in example 22BaAl4SiO12The XRD spectrum of the Ce and Cr fluorescent powder 2 is compared with that of a standard card.
FIG. 4 is Y obtained in example 22BaAl4SiO12Emission spectra of the Ce, Cr phosphor 2 and phosphor 1 of example 1 were compared.
FIG. 5 is Y obtained in example 32BaAl4SiO12:Ce，And the emission spectra of the light conversion film made of the Cr fluorescent powder and the epoxy resin glue, the fluorescent powder 1 and the fluorescent powder 2 are compared.
FIG. 6 is Y obtained in example 42BaAl4SiO12The emission spectra of the phosphor 2 and the light conversion film made of Ce, Cr phosphor 2 and epoxy resin glue are compared.
FIG. 7 is Y obtained in example 52BaAl4SiO12The emission spectra of the light conversion film made of Ce, Cr phosphor 2 and epoxy resin glue and phosphor 1 and phosphor 2 are compared.
FIG. 8 is Y obtained in example 62BaAl4SiO12Emission spectrum comparison chart of light conversion film made of Ce, Cr fluorescent powder 2 and epoxy resin glue and fluorescent powder 1 and fluorescent powder 2
FIG. 9 is a schematic diagram of the position relationship between the plants and the sun for arranging the film.
Detailed Description
Example 1
According to Y1.97BaAl3.95SiO120.03Ce, 0.05Cr in the stoichiometric ratio and 0.2224g of Y were weighed2O30.1973g of BaCO30.2015g of Al2O30.0601g of SiO20.0052g of CeO2And 0.0038g of Cr2O3The weighed raw materials are fully ground and uniformly mixed, then put into an alumina crucible, put into a tube furnace and heated at 1450 ℃ (volume percent is 5% H)2And 95% N2Atmosphere) for 4 hours (the preheating temperature of the tubular furnace is 200-300 ℃, the heating rate of the raw materials after being placed into the tubular furnace is 5 ℃/min), and the raw materials are cooled to room temperature along with the furnace to obtain a calcined substance; the obtained calcined product was ground to obtain phosphor 1. The XRD pattern of the phosphor 1 is shown in figure 1, wherein the peak shapes and peak positions of the peaks correspond to PDF cards one by one, and the phase of the prepared powder is proved to be single phase.
The excitation and emission spectra of the sample were then measured and, as seen in FIG. 2, the excitation spectrum showed the presence of three broad peaks with excitation peak peaks at 342nm, 450nm and 600nm, respectively, and the emission spectrum showed multiple emission peaks where there was a presence at 692nmIn a narrow peak and highest intensity. From the spectrogram we can find that Y1.97BaAl3.95Sio120.03Ce and 0.05Cr can be excited by light with the wavelength ranges of 310-380 nm, 380-520 nm and 520-660 nm, so that a wide excitation area is provided, and a sample can be absorbed in the ultraviolet light area of 310-380 nm, so that the film is prevented from being yellowed and disintegrated by sunlight; the sample emitted red light with wavelengths of about 683nm, 692nm, 710nm and 728nm in the luminescence spectrum.
Example 2
According to Y1.97BaAl3.95SiO120.03Ce, 0.05Cr in the stoichiometric ratio and 0.2224g of Y were weighed2O30.1973g of BaCO30.2015g of Al2O30.0601g of SiO20.0052g of CeO2And 0.0038g of Cr2O3And then 4wt% of AlF3The raw materials are fully ground and uniformly mixed as fluxing agent, then put into an alumina crucible, put into a tubular furnace and heated at 1450 ℃ (5% H)2And 95% N2Atmosphere) for 4 hours (the preheating temperature of the tubular furnace is 200-300 ℃, the heating rate of the raw materials after being placed into the tubular furnace is 5 ℃/min), and the raw materials are cooled to room temperature along with the furnace to obtain a calcined substance; the obtained calcined product was ground to obtain phosphor 2. The XRD spectrum of the phosphor 2 (as shown in fig. 3), the peak shapes and peak positions in the graph correspond to PDF cards one-to-one, which proves that the phase of the prepared powder is a single phase, and from the comparison of the emission spectrum of the phosphor 2 and the emission spectrum of the phosphor 1 (as shown in fig. 4), we can see that the luminous intensity of the phosphor is improved by 46.4% compared to the phosphor 1.
Example 3
The glue and the fluorescent powder are prepared into a film according to the proportion of 4: 1. The method specifically comprises the following steps: a, B g of each glue was weighed out to give 0.6g of the phosphor 2 prepared in example 2, and the mixture was stirred in a vacuum defoamer under vacuum (stirring time: 2min30 s). And (4) putting the uniformly stirred mixture into an oven for drying. After 6h, the dried membrane 1 was taken out and its emission spectrum under excitation at 450nm was measured, as shown in FIG. 5.
Example 4
The glue and the fluorescent powder are prepared into a film according to the proportion of 7:3, and the method specifically comprises the following steps: a, B g of glue is weighed, 0.45g of the phosphor 2 prepared in example 2 is added to the weighed epoxy resin glue, and the mixture is put into a vacuum defoaming machine to be stirred uniformly. And (4) putting the uniformly stirred mixture into an oven for drying. After 6h, the dried membrane 2 was taken out and its emission spectrum under excitation at 450nm was measured, as shown in FIG. 6.
Example 5
The glue and the fluorescent powder are prepared into a film according to the proportion of 2: 3. The method specifically comprises the following steps: a, B g of glue is weighed, 0.6g of the phosphor 2 prepared in example 2 is added to the weighed epoxy resin glue, and the mixture is placed in a vacuum defoaming machine for vacuum stirring. And (4) putting the uniformly stirred mixture into an oven for drying. After 6h, the dried membrane 3 was taken out and its emission spectrum under excitation at 450nm was measured, as shown in FIG. 7.
Example 6
The glue and the fluorescent powder are prepared into a film according to the proportion of 2: 3. The method specifically comprises the following steps: a, B g of glue was weighed, 0.75g of phosphor 2 prepared in example 2 was added to the weighed epoxy resin glue, and the mixture was placed in a vacuum defoaming machine and stirred under vacuum. And (4) putting the uniformly stirred mixture into an oven for drying. After 6h, the dried membrane 4 was taken out and its emission spectrum under excitation at 450nm was measured, as shown in FIG. 8.
The emission intensity of the phosphor prepared in example 2 and the emission intensity of the light conversion film prepared in examples 3, 4, 5, and 6 at 450nm were compared. From fig. 5 we can see that the luminescence intensity of the prepared film 1 is 36.9% and 55.2% of that of phosphor 2 and phosphor 1; from fig. 6 we can see that the luminescence intensity of the prepared film 1 is 56.6% and 84.7% of that of phosphor 2 and phosphor 1; from fig. 7 we can see that the luminescence intensity of the prepared film 1 is 71.4% and 107% of that of phosphor 2 and phosphor 1; from fig. 7, we can see that the luminescence intensity of the prepared film 1 is 76.7% and 115% of that of phosphor 2 and phosphor 1. From the results obtained above, it is obvious that the luminous intensity of the film continuously increases with the increase of the doping ratio of the fluorescent powder, when the ratio of the fluorescent powder in the film is more than 40%, the luminous intensity of the film exceeds the luminous intensity of the fluorescent powder 1, and the luminous intensity of the prepared 4 films exceeds 50% of the luminous intensity of the fluorescent powder 2, so that the expected effect is achieved, and the film can provide strong red light for plants, thereby promoting the growth of the plants.
Finally, we add an important annotation. The phosphor content is one hundred percent, while our film contains much less than one hundred percent phosphor. Thus, by exact comparison of the powder to a film having the same phosphor concentration, we can clearly see that our film has a higher deep red brightness than the phosphor powder, as shown in the graph. The invention has the advantage that the total reflection of the light emitted in the fluorescent powder is greatly reduced by the method of wrapping the fluorescent powder by the polymer resin with the refractive index almost the same as that of the fluorescent powder.
Claims (7)
1. A light conversion film capable of promoting plant growth is characterized in that: the light conversion film is in the form of film with thickness of mum level and contains component Y(3-x)BaxAl(5-x)SixO12mCE, nCr, 0 ≦ x ≦ 1, m > 0, n > 0, and a polymer resin or glass having a refractive index of 1.4 to 1.65, the garnet phosphor being uniformly dispersed in the polymer resin or glass.
2. The light conversion film according to claim 1, wherein the light conversion film is characterized in that: the garnet phosphor has a maximum emission peak in the region of 660-700 nm.
3. The light conversion film according to claim 1, wherein the light conversion film is characterized in that: the polymer resin is polycarbonate or epoxy resin.
4. A preparation method of a light conversion film capable of promoting plant growth is characterized by comprising the following steps: step 1) according to the expression Y(3-x)BaxAl(5-x)SixO12mCE, nCr, x is less than or equal to 0 and less than or equal to 1, m is more than 0, n is more than 0, and the following raw materials are respectively weighed according to the stoichiometric ratio of each chemical composition:
yttrium compound: using yttrium oxide Y2O3Or yttrium-containing hydroxides or nitrates, carbonates or sulfates or phosphates;
an aluminum compound: using yttrium oxide Al2O3Or aluminium-containing hydroxides or nitrates or sulphates or phosphates;
a barium compound: by using barium carbonate BaCO3Or a barium-containing hydroxide or a barium-containing nitrate or a barium-containing sulfate or a barium-containing phosphate;
silicon compound (b): using silicon dioxide SiO2Or a silicon-containing hydroxide or a silicon-containing nitrate or a silicon-containing carbonate or a silicon-containing sulfate or a silicon-containing phosphate;
a chromium compound: using chromium oxide Cr2O3Or chromium-containing hydroxides or nitrates, carbonates or sulfates or phosphates;
a cerium compound: using cerium oxide CeO2Or a cerium-containing hydroxide or nitrate, a cerium-containing carbonate or a cerium-containing sulfate or a cerium-containing phosphate;
mixing the weighed raw material components together and grinding the mixture to micron level to obtain mixed raw material powder;
step 2): calcining the mixed raw material powder obtained in the step 1) in a reducing atmosphere at the temperature of 1400-1500 ℃ for 4-5 hours; cooling the calcined material to room temperature along with the furnace to obtain a calcined substance;
and step 3: grinding the calcined substance to micron level to obtain fluorescent powder containing Ce and Cr in a garnet structure, mixing the fluorescent powder with polymer resin according to the mass ratio of 1: 4-1: 1, and preparing the light conversion film according to the existing film preparation process.
5. The method of claim 4, wherein the step of preparing a light conversion film for promoting plant growth comprises: the reducing atmosphere adopts the following gases: ammonia NH3Or 5 to 25% by volume of hydrogen H2And 95-75% of nitrogen N2OfA mixed gas, or a mixture of 5 to 25% by volume of CO and 95 to 75% by volume of N2The composition of the mixed gas.
6. The method of claim 4, wherein the step of preparing a light conversion film for promoting plant growth comprises: the polymer resin is epoxy A, B glue, epoxy A, B glue is mixed according to the mass ratio of 1:1, the fluorescent powder and the mixed glue are mixed according to the mass ratio of 1: 4-1: 1, then the mixture is stirred in a vacuum defoaming machine for 2.5 minutes, after being uniformly stirred, the mixture is placed in an oven to be dried, and the dried material is attached to the plate through a coating machine.
7. The method of claim 4, wherein the step of preparing a light conversion film for promoting plant growth comprises: adding 4wt% of AlF3Fluxing agent, AlF3Mixing with the weighed raw materials, and grinding.
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| PCT/CN2021/104104 WO2022002217A1 (en) | 2020-07-03 | 2021-07-01 | Light conversion film capable of promoting plant growth and preparation method therefor |
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| CN112779010A (en) * | 2021-01-27 | 2021-05-11 | 中国科学院长春应用化学研究所 | Near-infrared luminescent material, preparation method thereof and near-infrared LED |
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| CN112625682A (en) * | 2020-12-09 | 2021-04-09 | 北京科技大学 | Cr3+Doped phosphate-based far-red light-near infrared luminescent material and preparation method thereof |
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| CN113150783A (en) * | 2021-04-27 | 2021-07-23 | 中国科学院长春应用化学研究所 | Color-adjustable afterglow luminescent material, preparation method thereof and lighting product |
| CN113150783B (en) * | 2021-04-27 | 2022-11-01 | 中国科学院长春应用化学研究所 | Color-adjustable afterglow luminescent material, preparation method thereof and lighting product |
| CN113248926A (en) * | 2021-05-06 | 2021-08-13 | 甘肃颐年商贸有限责任公司 | Red light conversion film capable of promoting plant growth and preparation method thereof |
| CN113402744A (en) * | 2021-05-06 | 2021-09-17 | 甘肃颐年商贸有限责任公司 | Light conversion film capable of promoting plant growth and preparation method and application thereof |
| CN113248926B (en) * | 2021-05-06 | 2023-11-24 | 甘肃颐年商贸有限责任公司 | Red light conversion film capable of promoting plant growth and preparation method thereof |
| CN114920463A (en) * | 2022-03-11 | 2022-08-19 | 上海应用技术大学 | Garnet type fluorescent glass ceramic and preparation method thereof |
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| WO2022002217A1 (en) | 2022-01-06 |
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Application publication date: 20201103 |