CN1176182C - Multi-kernel rare-earth light-converting powder, its preparing process and its application - Google Patents
Multi-kernel rare-earth light-converting powder, its preparing process and its application Download PDFInfo
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- CN1176182C CN1176182C CNB001195921A CN00119592A CN1176182C CN 1176182 C CN1176182 C CN 1176182C CN B001195921 A CNB001195921 A CN B001195921A CN 00119592 A CN00119592 A CN 00119592A CN 1176182 C CN1176182 C CN 1176182C
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Abstract
The present invention discloses a rare earth light-converting powder for converting ultraviolet light to red light, a preparation method and the application on plastic films thereof. The polynucleation rare earth light-converting powder is represented by the chemical formula Eu<x>(m<1>)<y>(m<2>)<z>li. In the formula, M<1> represents samarium or trivalent cerium; M<2> represents lanthanum or yttrium or gadolinium; L is ligand which is selected from carboxylate radicals of the following carboxylic acids, such as aromatic formic acid, acetic acid, dicarboxylic acid, triformic acid and aromatic formic acid substituted by methyl or ethyl or amido; x=0.01 to 0.08, y=0.01 to 0.20 and z=1-x-y; when the ligand L is monoacid, i is equal to 3; when the ligand L is dibasic acid, i is equal to 1.5; when the ligand L is tribasic acid, i is equal to 1. A produced light-converting agricultural film or a light-converting no-drip weathering agricultural film can convert ultraviolet light in solar radiation to the red light if the polynucleation rare earth light-converting powder serves as an additive. A field experiment indicates that the rare earth light-converting powder can promote plant growth, enhance crop output and improve crop quality.
Description
Technical field
The present invention relates to multi-kernel rare-earth light-converting powder, its preparation method and application thereof, be specifically related to be used for UV-light is converted to multi-kernel rare-earth light-converting powder, its preparation method and the application on plastics film thereof of ruddiness.
Background technology
Modern agriculture has been extensive use of plastic sheeting for farm use, and ordinary agricultural membrane and long-lived dropless agricultural film have been arranged.Ordinary agricultural membrane has the transparent heat insulating effect, has also added protective agent (as antioxidant) and antifogging agent in the long-lived dropless agricultural film usually, makes it except the energy transparent heat insulating, also has performance weather-proof, no droplet.But,, wish that also plastic sheeting for farm use has the performance that UV-light can be converted to ruddiness along with Agricultural Development.Because plant-growth and photosynthesis are closely related, plant is to utilize intravital chlorophyll to catch luminous energy to carry out photosynthetic.UV-light can not be utilized by plant absorbing, and that ruddiness is photosynthesis of plant is needed.
Developed some light-converting powders, they can convert the UV-light in the solar radiation to ruddiness.Usually only contain a kind of rare earth element (as europium) that can send fluorescence in the present existing light-converting powder, also have some to contain two kinds of rare earth elements.Because the europium ion that has used high level in these light-converting powders is as luminescent activator, and europium is very expensive, has therefore improved the cost of light-converting powder greatly, makes it be difficult to carry out practical application.
In addition, existing light-converting powder converts UV-light to the narrower ruddiness of emmission spectrum usually.For example, the light-converting powder used of the Chinese plastic sheeting for farm use of " plastics " magazine the 25th interim report in 1996 is transformed into the UV-light in the solar radiation ruddiness of 600-630nm.The single ruddiness of this narrower wave band not exclusively has the feature of bionical attitude, and is unsatisfactory for the growth that promotes plant.
In addition, present existing light-converting powder is generally used for ordinary agricultural membrane and makes optical transfer agricultural film.But, seldom have light-converting powder is added the report that long-lived dropless agricultural film makes a light conversion nothing weather-proof plastic sheeting for farm use.Reason is that protective agent or the antifogging agent in the long-lived dropless agricultural film can influence the commentaries on classics optical property that has light-converting powder.A kind of light conversion film with anti-aging and antifogging property has been described in the Chinese patent application 94114161.6, but must carry out the strictness screening to protective agent and antifogging agent, in specification sheets, only point out three kinds of optional protective agents and two kinds of optional antifogging agents.
Summary of the invention
The purpose of this invention is to provide a kind of low cost, high efficiency multi-kernel rare-earth light-converting powder, it can be converted to the UV-light in the solar radiation ruddiness of emission band broad effectively, and have excellent compatibility with plastics film, can be applicable to the conversion of optical transfer agricultural film and light does not have the weather-proof plastic sheeting for farm use of dripping.
Another object of the present invention provides the preparation method of multi-kernel rare-earth light-converting powder.
A further object of the invention is that multi-kernel rare-earth light-converting powder is applied to plastics film.
A further object of the invention is that multi-kernel rare-earth light-converting powder is applied to multiple plastic sheeting for farm use, comprises an optical transfer agricultural film and light conversion nothing weather-proof plastic sheeting for farm use.
The invention provides a kind of multi-kernel rare-earth light-converting powder, by chemical formula Eu
x(M
1)
y(M
2)
zL
iExpression, M in the formula
1Be samarium or trivalent cerium; M
2Be lanthanum, yttrium or gadolinium; L is a part, is selected from the carboxylate radical of following carboxylic acid: aromatics formic acid, aromatics acetate, aromatic dicarboxylic acid, aromatics tricarboxylic acid and the aromatics formic acid that is replaced by methyl, ethyl or amino; X=0.01-0.08; Y=0.01-0.20; Z=1-x-y; When ligand L is monoprotic acid, i=3, during diprotic acid, i=1.5, during triprotic acid, i=1.
The carboxylic acid that can be used as the L part is aromatics formic acid, aromatics acetate, aromatic dicarboxylic acid, aromatics tricarboxylic acid and by methyl, ethyl or the amino aromatics formic acid that replaces.For example, naphthoic acid, naphthylacetic acid, phenylformic acid, toluylic acid, phthalic acid, benzene tricarboxylic acid, tolyl acid, ethyl benzoate, benzaminic acid etc.
The concrete principle that rare-earth light-converting powder can be converted to UV-light ruddiness is: utilize the triplet excited state of organic ligand and the energy level coupling of rare earth ion excited state, part is after the near ultraviolet region absorbs energy excitation, by triplet state in non-radiative mode through intersystem crossing, excitation energy is passed to rare earth ion, rare earth ion transits to than low-lying level with radiation mode again, send characteristic fluorescence thus, this luminous intensity specific ionization rare earth ion has obvious enhancing.
The present inventor finds through further investigation with to a large amount of selection tests back of rare earth ion, though itself does not produce fluorescence rare-earth elements of lanthanum, yttrium and gadolinium, but will can make the luminous intensity of europium ion stronger in their adding light-converting powders, this be also referred to as " effect concentrates ".The adding of lanthanum, yttrium or gadolinium element can also significantly reduce the consumption of europium except the luminous intensity that can improve light-converting powder, greatly reduce the cost of light-converting powder thus.The present inventor also finds, element samarium or trivalent cerium are added in the light-converting powder, and the scope that can regulate emmission spectrum also can reduce the consumption of europium on the other hand on the one hand, thereby reduces the cost of light-converting powder.
The present inventor finds through behind a large amount of composition proportioning tests that again the multi-kernel rare-earth light-converting powder with the present invention's composition can be realized purpose of the present invention.
Therefore, multi-kernel rare-earth light-converting powder of the present invention has plurality of advantages.It contains at least three kinds of rare earth elements, and wherein the content of europium is minimum, only is the 0.01-0.08 mole, greatly reduces the cost of light-converting powder thus.Multi-kernel rare-earth light-converting powder of the present invention produces bright-coloured ruddiness under the irradiation of ultraviolet lamp, illustrate that it can convert UV-light to ruddiness effectively.Under the effect of 240nm excitation wavelength, produce the emmission spectrum of 580-720nm, its emission band is wider than existing light-converting powder far away, so have more bionical characteristic, more helps plant-growth.With pure Eu
2O
3Luminous intensity be benchmark, the luminous intensity of multi-kernel rare-earth light-converting powder of the present invention is its 22 times.In addition, multi-kernel rare-earth light-converting powder of the present invention and plastics film have good consistency, it can not only be used for ordinary agricultural membrane and make optical transfer agricultural film, can also be widely used in long-lived weather-proof plastic sheeting for farm use, making the light conversion does not have the weather-proof plastic sheeting for farm use of dripping, and its performance is not subjected to the influence (specifically seeing the test-results data among the embodiment) of other additive in the plastic sheeting for farm use.
The present invention also provides the method for preparing above-mentioned multi-kernel rare-earth light-converting powder, and this method comprises that preparation contains each component metals ion Eu, M of required stoichiometric ratio
1And M
2Acidic aqueous solution, the carboxylic acid that will contain in addition the L part adds in the entry, regulates pH value to greater than 6, obtains ligand solution, and above-mentioned solution is reacted, and produces precipitation, filtration, drying obtain white powder.
An embodiment of this method is that the oxide compound that will contain each component metals of required stoichiometric ratio is dissolved in the strong acid, in addition part is added in the entry, regulates the pH value extremely greater than 6, obtain ligand solution, two kinds of solution are reacted, produce precipitation, filtration, drying obtain white powder.Wherein, strong acid can be hydrochloric acid or nitric acid.Water can be distilled water, pure water or deionized water.
When needs add cerium, use the solution of cerous nitrate, it is reacted with above-mentioned two kinds of solution, produce precipitation, filtration, drying obtain white powder.
Preparation method of the present invention is easy to operate, and is simple, can make light-converting powder with low cost.
The present invention also comprises multi-kernel rare-earth light-converting powder is used for plastics film, comprises plastic sheeting for farm use, anti-counterfeit package film and antiultraviolet film etc.Multi-kernel rare-earth light-converting powder of the present invention can be widely used in plastic sheeting for farm use, and light-converting powder as additive, is used and produced ordinary agricultural membrane or the identical production unit of long-lived dropless agricultural film, produces optical transfer agricultural film respectively or the light conversion does not have the weather-proof plastic sheeting for farm use of dripping with ordinary method.The mechanical property of the plastic sheeting for farm use that makes is consistent with ordinary agricultural membrane or long-lived dropless agricultural film, reaches national GB4455-94 standard; And the UV-light in the solar radiation can be converted to ruddiness, thereby promote plant-growth, improve crop yield, improve crop quality.
Embodiment
The invention will be further described by the following examples.Should be appreciated that embodiment is illustrative, and the present invention is not provided constraints.
Embodiment 1
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.0025mol Eu
2O
3, 0.005molSm
2O
3, 0.0425mol La
2O
3) and the 0.3mol phenylformic acid.With each component metals oxide compound heating for dissolving in hydrochloric acid, in addition phenylformic acid is added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content that records this powder with weighting method GB/T12687.1-90 (down together) is 30.8% (weight) (calculated value is 32.7%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.05Sm
0.10La
0.85L
3Consistent.
Embodiment 2
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.002mol Eu
2O
3, 0.003molSm
2O
3, 0.045mol La
2O
3) and the 0.3mol phenylformic acid.With each component metals oxide compound heating for dissolving in hydrochloric acid, in addition phenylformic acid is added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.3.The rare earth oxide total content that records this powder with weighting method is 30.3% (weight) (calculated value is 32.6%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.04Sm
0.06La
0.90L
3Consistent.
Embodiment 3
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.001mol Eu
2O
3, 0.009molSm
2O
3, 0.040mol La
2O
3) and the 0.3mol naphthoic acid.With each component metals oxide compound heating for dissolving in hydrochloric acid, in addition naphthoic acid is added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.5.The rare earth oxide total content that records this powder with weighting method is 23.7% (weight) (calculated value is 25.2%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.02Sm
0.18La
0.80L
3Consistent.
Embodiment 4
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.0005mol Eu
2O
3, 0.0005molSm
2O
3, 0.049mol La
2O
3) and the 0.3mol naphthylacetic acid.With each component metals oxide compound heating for dissolving in hydrochloric acid, in addition naphthylacetic acid is added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.4.The rare earth oxide total content that records this powder with weighting method is 22.2% (weight) (calculated value is 23.5%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.01Sm
0.01La
0.98L
3Consistent.
Embodiment 5
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.004mol Eu
2O
3, 0.010molSm
2O
3, 0.036mol La
2O
3) and 0.1mol 1,3, the 5-benzene tricarboxylic acid.With each component metals oxide compound heating for dissolving in nitric acid, in addition with 1,3, the 5-benzene tricarboxylic acid adds in the deionized water, and heating is also regulated the pH value to greater than 6, obtains ligand solution, above-mentioned two kinds of solution are reacted, produce precipitation, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content that records this powder with weighting method is 45.4% (weight) (calculated value is 47.6%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.08Sm
0.20La
0.72L
1Consistent.
Embodiment 6
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.0035mol Eu
2O
3, 0.0075molSm
2O
3, 0.039mol La
2O
3) and the 0.3mol toluylic acid.With each component metals oxide compound heating for dissolving in nitric acid, in addition toluylic acid is added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.0.The rare earth oxide total content that records this powder with weighting method is 28.6% (weight) (calculated value is 30.1%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.07Sm
0.15La
0.78L
3Consistent.
Embodiment 7
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.001mol Eu
2O
3, 0.001molSm
2O
3, 0.048mol La
2O
3) and the 0.15mol phthalic acid.With each component metals oxide compound heating for dissolving in nitric acid, in addition phthalic acid is added in the distilled water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content that records this powder with weighting method is 40.1% (weight) (calculated value is 42.4%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.02Sm
0.02La
0.96L
1.5Consistent.
Embodiment 8
By required stoichiometric ratio, take by weighing each component metals oxide compound (0.003mol Eu
2O
3, 0.010molSm
2O
3, 0.037mol La
2O
3) and the 0.3mol anthranilic acid.With each component metals oxide compound heating for dissolving in hydrochloric acid, in addition anthranilic acid is added in the distilled water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned two kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.1.The rare earth oxide total content that records this powder with weighting method is 28.3% (weight) (calculated value is 30.2%), water content＜2%.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.06Sm
0.20La
0.74L
3Consistent.
Embodiment 9-16
Carry out embodiment 9-16 according to embodiment 1-8 respectively, different is with metal oxide La
2O
3Replace with Y
2O
3, all the other steps are corresponding identical respectively.Obtain white powder thus, the pH value is in the scope of 6.0-6.5.The rare earth oxide total content and the calculated value of the powder that records with weighting method are approaching.The powder constituent that records with atomic absorption spectrometry and plasma method corresponds respectively to the result among the embodiment 1-8, and La becomes Y in just forming.
Embodiment 17-24
Carry out embodiment 17-24 according to embodiment 1-8 respectively, different is with metal oxide La
2O
3Replace with Gd
2O
3, all the other steps are corresponding identical respectively.Obtain white powder thus, the pH value is in the scope of 6.0-6.5.The rare earth oxide total content and the calculated value of the powder that records with weighting method are approaching.The powder constituent that records with atomic absorption spectrometry and plasma method corresponds respectively to the result among the embodiment 1-8, and La becomes Gd in just forming.
Embodiment 25
By required stoichiometric ratio, take by weighing 0.0025mol Eu
2O
3, 0.010mol Ce (NO
3)
3, 0.0425molLa
2O
3With the 0.3mol phenylformic acid.With Eu
2O
3And La
2O
3Heating for dissolving in hydrochloric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with deionized water, in addition phenylformic acid added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.05Ce
0.10La
0.85L
3Consistent.
Embodiment 26
By required stoichiometric ratio, take by weighing 0.002mol Eu
2O
3, 0.006mol Ce (NO
3)
3, 0.045molLa
2O
3With the 0.3mol o-ethylbenzoic acid.With Eu
2O
3And La
2O
3Heating for dissolving in hydrochloric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with deionized water, in addition o-ethylbenzoic acid added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.3.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.04Ce
0.06La
0.90L
3Consistent.
Embodiment 27
By required stoichiometric ratio, take by weighing 0.001mol Eu
2O
3, 0.018mol Ce (NO
3)
3, 0.040molLa
2O
3With the 0.3mol naphthoic acid.With Eu
2O
3And La
2O
3Heating for dissolving in hydrochloric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with deionized water, in addition naphthoic acid added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.5.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.02Ce
0.18La
0.80L
3Consistent.
Embodiment 28
By required stoichiometric ratio, take by weighing 0.0005mol Eu
2O
3, 0.001mol Ce (NO
3)
3, 0.049molLa
2O
3With the 0.3mol gavaculine.With Eu
2O
3And La
2O
3Heating for dissolving in hydrochloric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with deionized water, in addition gavaculine added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.4.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.01Ce
0.01La
0.98L
3Consistent.
Embodiment 29
By required stoichiometric ratio, take by weighing 0.004mol Eu
2O
3, 0.020mol Ce (NO
3)
3, 0.036molLa
2O
3With 0.1mol 1,2, the 3-benzene tricarboxylic acid.With Eu
2O
3And La
2O
3Heating for dissolving in nitric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with deionized water, in addition with 1,2, the 3-benzene tricarboxylic acid adds in the distilled water, and heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.08Ce
0.20La
0.72L
1Consistent.
Embodiment 30
By required stoichiometric ratio, take by weighing 0.0035mol Eu
2O
3, 0.015mol Ce (NO
3)
3, 0.039molLa
2O
3With the 0.3mol toluylic acid.With Eu
2O
3And La
2O
3Heating for dissolving in nitric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with distilled water, in addition toluylic acid added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.0.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.07Ce
0.15La
0.78L
3Consistent.
Embodiment 31
By required stoichiometric ratio, take by weighing 0.001mol Eu
2O
3, 0.002mol Ce (NO
3)
3, 0.048molLa
2O
3With the 0.15mol m-phthalic acid.With Eu
2O
3And La
2O
3Heating for dissolving in nitric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with distilled water, in addition m-phthalic acid added in the deionized water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.2.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.02Ce
0.02La
0.96L
1.5Consistent.
Embodiment 32
By required stoichiometric ratio, take by weighing 0.003mol Eu
2O
3, 0.020mol Ce (NO
3)
3, 0.037molLa
2O
3With the 0.3mol m-methyl benzoic acid.With Eu
2O
3And La
2O
3Heating for dissolving in hydrochloric acid is with Ce (NO
3)
3Be mixed with the aqueous solution with distilled water, in addition m-methyl benzoic acid added in the distilled water, heating is also regulated pH value to greater than 6, obtains ligand solution, and above-mentioned three kinds of solution are reacted, and produces and precipitates, after filtration, obtain white powder after the drying.The pH value of this powder is 6.1.The rare earth oxide total content and the calculated value that record this powder with weighting method are approaching.The powder constituent and the chemical formula Eu that record with atomic absorption spectrometry and plasma method
0.06Ce
0.20La
0.74L
3Consistent.
Embodiment 33-40
Carry out embodiment 33-40 according to embodiment 25-32 respectively, different is with metal oxide La
2O
3Replace with Y
2O
3, all the other steps are corresponding identical respectively.Obtain white powder thus, the pH value is in the scope of 6.0-6.5.The rare earth oxide total content and the calculated value of the powder that records with weighting method are approaching.The powder constituent that records with atomic absorption spectrometry and plasma method corresponds respectively to the result among the embodiment 25-32, and La becomes Y in just forming.
Embodiment 41-48
Implement 41-48 according to embodiment 25-32 respectively, different is with metal oxide La
2O
3Replace with Gd
2O
3, all the other steps are corresponding identical respectively.Obtain white powder thus, the pH value is in the scope of 6.0-6.5.The rare earth oxide total content and the calculated value of the powder that records with weighting method are approaching.The powder constituent that records with atomic absorption spectrometry and plasma method corresponds respectively to the result among the embodiment 25-32, and La becomes Gd in just forming.
The multi-kernel rare-earth light-converting powder that each embodiment is made is as additive, uses respectively and produces ordinary agricultural membrane or the identical production unit of long-lived dropless agricultural film, produces optical transfer agricultural film or the light conversion does not have the weather-proof plastic sheeting for farm use of dripping with ordinary method.The gained plastic sheeting for farm use is carried out fluorescence property check and agricultural experiment.The ordinary agricultural membrane or the long-lived dropless agricultural film that do not add multi-kernel rare-earth light-converting powder are used as control film.
[fluorescence property check]
Do not have the weather-proof plastic sheeting for farm use (experimental film hereinafter referred to as) of dripping with multi-kernel rare-earth light-converting powder, optical transfer agricultural film and light conversion that the UV-irradiation embodiment of 254nm makes, all produce macroscopic bright-coloured ruddiness, and control film does not produce ruddiness.
Fluorescence emission spectrum with fluorescence spectrophotometer test light-converting powder and experimental film.Under the effect of 240nm excitation wavelength, light-converting powder and experimental film have all produced the characteristic fluorescence emmission spectrum of europium (III) element in the 580-720nm scope.Wherein, the fluorescence emission peak wavelength is that the fluorescence relative intensity of 612nm is the strongest.The emitting red light bands of a spectrum that experimental film produces under ultraviolet excitation just in time are complementary with the absorption spectrum and the photosynthetic special wavelength of plant chlorophyll, thereby can promote plant growth.Other auxiliary agents such as the photostabilizer that is added in the experimental film, antioxidant and antifogging agent do not disturb the light conversion performance of multi-kernel rare-earth light-converting powder of the present invention.
[crop early yield test in the canopy]
Early yield to crop in the canopy of use-testing film is tested, when optical transfer agricultural film during as experimental film, with ordinary agricultural membrane film CK in contrast
1When light conversion does not have the weather-proof plastic sheeting for farm use (UTR) of dripping as experimental film, with long-lived dropless agricultural film film CK in contrast
2Test-results is as shown in table 1, and data are the test mean value of the experimental film that makes of the multi-kernel rare-earth light-converting powder of the various embodiments described above in the table.By data in the table as seen, the crop early yield obviously increases production in the canopy of use-testing film.
Table 1
| Crop | The experimental film classification | The control film classification | Output (kilogram/mu) | Stimulation ratio (%) | |
| Experimental film | Control film | ||||
| Tomato | Optical transfer agricultural film | CK 1 | 466.35 | 385.25 | 21.68 |
| Eggplant | Optical transfer agricultural film | CK 1 | 873.5 | 785.1 | 11.25 |
| Strawberry | Optical transfer agricultural film | CK 1 | 547.2 | 440.7 | 24.17 |
| Eggplant | UTR | CK 2 | 814.2 | 614.8 | 32.42 |
| Muskmelon | UTR | CK 2 | 2552.6 | 2219.2 | 15.04 |
[attribute test of crop in the canopy]
Quality to crop in the canopy of use-testing film is tested, and the light conversion is not had the weather-proof plastic sheeting for farm use (UTR) of dripping as experimental film, and long-lived dropless agricultural film is film CK in contrast
2Test-results is as shown in table 2, and data are the test mean value of the experimental film that makes of the multi-kernel rare-earth light-converting powder of the various embodiments described above in the table.By data in the table as seen, sugar, starch and the protein content of crop all are significantly increased in the canopy of use-testing film.
Table 2
| Crop | Use film | Soluble sugar % | Starch % | Protein % |
| Eggplant | UTR | 6.593 | 5.934 | 46.780 |
| CK 2 | 6.094 | 5.485 | 39.899 | |
| Tomato | UTR | 7.905 | 7.115 | 31.906 |
| CK 2 | 6.896 | 6.206 | 29.706 | |
| Watermelon | UTR | 7.761 | 6.985 | 27.221 |
| CK 2 | 7.292 | 6.563 | 25.141 | |
| Muskmelon | UTR | 3.431 | 3.088 | 33.194 |
| CK 2 | 3.270 | 2.943 | 30.425 |
[effect test of the interior crop situation of situation and canopy in the canopy]
The use-testing film is tested crop situation in situation in the canopy and the canopy, when optical transfer agricultural film during as experimental film, with ordinary agricultural membrane film CK in contrast
1When light conversion does not have the weather-proof plastic sheeting for farm use (UTR) of dripping as experimental film, with long-lived dropless agricultural film film CK in contrast
2Test-results is as shown in table 3, and data are the test mean value of the experimental film that makes of the multi-kernel rare-earth light-converting powder of the various embodiments described above in the table.
Table 3
| Test event | Optical transfer agricultural film/CK 1Film | UTR film/CK 2Film |
| Transmittance amplification | 5-15％ | 3-4％ |
| The canopy temperature rise | 1-3℃ | 1-3℃ |
| Chlorophyll content in leaf blades amplification | 13.08％ | 5.94％ |
| Crop absorbs nutrient rate of increase nitrogen phosphorus potassium | 6.91％ 0.33％ 0.87％ | 6.01％ 0.58％ 2.35％ |
| Crop and fruit quality sugar rate of increase vitamins C rate of increase | 7.93% (strawberry) 18.80% (strawberry) | 4.65% (watermelon) 18.18% (watermelon) |
| The crop yield amplitude | 5-14％ | 8-14％ |
| Input-output ratio | 1∶2.8-1∶12 | 1∶3.9-1∶7.2 |
Claims (5)
1. multi-kernel rare-earth light-converting powder is by chemical formula Eu
x(M
1)
y(M
2)
zL
iExpression, M in the formula
1Be samarium or trivalent cerium; M
2Be lanthanum, yttrium or gadolinium; L is a part, is selected from the carboxylate radical of following carboxylic acid: aromatics formic acid, aromatics acetate, aromatic dicarboxylic acid, aromatics tricarboxylic acid and the aromatics formic acid that is replaced by methyl, ethyl or amino; X=0.01-0.08; Y=0.01-0.20; Z=1-x-y; When ligand L is monoprotic acid, i=3, during diprotic acid, i=1.5, during triprotic acid, i=1.
2. multi-kernel rare-earth light-converting powder as claimed in claim 1 is characterized in that the L part is selected from the carboxylate radical of following carboxylic acid: naphthoic acid, naphthylacetic acid, phenylformic acid, toluylic acid, phthalic acid, benzene tricarboxylic acid, tolyl acid, ethyl benzoate, benzaminic acid.
3. method for preparing the described multi-kernel rare-earth light-converting powder of claim 1, this method comprise that preparation contains each component metals ion Eu, M of required stoichiometric ratio
1And M
2Acidic aqueous solution, the carboxylic acid that will contain in addition the L part adds in the entry, regulates pH value to greater than 6, obtains ligand solution, and above-mentioned solution is reacted, and produces precipitation, filtration, drying obtain white powder, wherein M
1, M
2With identical in the implication of L and the claim 1.
4. the described multi-kernel rare-earth light-converting powder of claim 1 is used for the application of plastics film as additive.
5. the described multi-kernel rare-earth light-converting powder of claim 1 is used for the application of plastic sheeting for farm use as additive.
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| CNB001195921A CN1176182C (en) | 2000-08-10 | 2000-08-10 | Multi-kernel rare-earth light-converting powder, its preparing process and its application |
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|---|---|---|---|
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|---|---|
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| CN1176182C true CN1176182C (en) | 2004-11-17 |
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| CN100348692C (en) * | 2005-06-13 | 2007-11-14 | 上海师范大学 | Broad ultraviolet or yellow green light conversion to red blue light nanometer material and its preparation method |
| CN106947462A (en) * | 2017-05-11 | 2017-07-14 | 长春工业大学 | A kind of rare earth organic light conversion agents and preparation method thereof |
| CN109181059A (en) * | 2018-08-03 | 2019-01-11 | 东莞市济丰农业生态园开发有限公司 | It is a kind of to increase awning film of crop yield and preparation method thereof |
| CN112322291B (en) * | 2020-11-27 | 2023-03-14 | 崔明斌 | Dual-waveband agricultural greenhouse film fluorescent light conversion powder and preparation method thereof |
| CN113480997A (en) * | 2021-07-09 | 2021-10-08 | 济南大学 | Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof |
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