CN101126025B - Red light fluorescent powder and multilayer light conversion film - Google Patents
Red light fluorescent powder and multilayer light conversion film Download PDFInfo
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- CN101126025B CN101126025B CN2007101523177A CN200710152317A CN101126025B CN 101126025 B CN101126025 B CN 101126025B CN 2007101523177 A CN2007101523177 A CN 2007101523177A CN 200710152317 A CN200710152317 A CN 200710152317A CN 101126025 B CN101126025 B CN 101126025B
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Abstract
The invention relates to a red-light phosphor powder which consists of strontium of rare earth element and/or hafnium sulfides and activator. The invention is characterized in that: the adopted materials are fluorine sulfur oxides of lanthanum-yttrium-zirconium and/or hafnium. The total stoichiometric formula is (La1-x-y-zYxAyMez+4O)2S1(F-1)2z. The activator originates from the formula: A=(TR+3= Signa Eu, Sm, Gd, Tb)+(TR+4=Pr+4); in this situation, Me+4=Zr+4 and/or Hf+4. Compared with criterion material, the luminous brightness of the phosphor in the invention is increased by 1.6-2.4 times. In addition, the average diameter of red-light phosphor powder is d50 0.6 Mu m. The invention also discloses a light-conveying film of multilayer light, the three-layer polymerization agricultural filmof which is filled with phosphor powder. The agricultural film takes polyethylene and derivatives of that as matrix and is added with light stabilizer.
Description
[technical field that the present invention belongs to]
The present invention system is about a kind of optical material technical field.Particularly, be meant a kind of red light fluorescent powder and multilayer light conversion film, comprising fluorescent RE powder, the fluorescent material that it is used for the cathode-luminescence powder of colour crt screen and is used for luminescent lamp, also above-mentioned fluorescent RE powder can be applied as the luminescent conversion material be polymer thin film or non-textile materials in the present invention in addition, adopted with the covering plastic sheeting for farm use as greenhouse, hotbed (closed device).
[prior art]
With a large amount of uses to come from polyethylene, polyvinyl chloride, polypropylene printing opacity plastic sheeting for farm use the same, the light conversion agricultural film is widely used now, it can create sufficiently stable microclimate in hotbed and greenhouse.It helps to protect rice shoot and farm crop in time-division first frost in spring, summer growth cycle can significantly promote temperature.Now, the application of light conversion agricultural film is widely used.
The mechanism of these materials can be converted to shortwave-be mainly solar radiation ultraviolet part (is～6% in this light branch of earth middle latitude rate) the photosynthesis spectrum in the red and garnet zone of visible spectrum based on the particulate inorganic fluorescent material of being filled in the plastic sheeting for farm use volume.Red spectrum-also be that Russian natural scientist K.A. Ji Miliyazefu finds is for photosynthesis and carbohydrate (mainly are glucose C
6H
12O
6) basis that forms, wherein come from the formation chemical formula of the carbohydrate of carbonic acid gas and water:
6CO
2+6H
2O—→C
6H
12O
12+6O
2↑。
Photosynthesis is littler in the blue spectral region activity, yet but required for green plants nutritive issue formation (root system, leaf etc.).On the other hand, by what K.A. Ji Miliyazefu and other biological scholar established be, spectrum green-orange zone, light only influences the photosynthesis of certain plants, and they replace main green pigment α or β-chlorophyll, and occupying the majority is that the pigment of beta-yl matter (please refer to " light conversion agricultural film nanometer technology " international conference data that one of the contriver Suo Xin N.P. of this case is shown, Moscow, nano industrial, 2006, the 124-140 page or leaf).
Widespread use polymerization plastic sheeting for farm use can make in the closed soil device green plants obtain to stablize photosynthetic effect; this plastic sheeting for farm use is protected (please refer to No. 2160289 patent of Russia that one of the contriver Suo Xin N.P. of this case is won) by Russ P 2160289; this patent has disclosed the polyethylene polymerization film of trade mark for " good harvest ", is filled with Y in this film
2O
2S:Eu substrate fluorescent powder powder, its rete concentration are 100～150 μ m, and have a series of superiority in closed soil device: harvested ripe shortening 1.5-2 week in cycle the first time 1.; 2. vegetables, berry, industrial crops output are significantly promoted 25-75%; 3. with 5-8 ℃ of plant temperature increase in vegetative period in spring; And 4. make plant avoid the sun to burn.
Meanwhile, except be confirmed and predictable result, the photo bio effect of known plastic sheeting for farm use also has the advantage of unanticipated.Comprising, it can promote 1～2 times with vitamins C in berry, vegetables and the fruit and micro element content.We interrelate this effect and following element usually, i.e. wavelength X=626nm zone Y
2O
2S:Eu matrix inorganic fluorescent powder has very narrow emission band.Be equal to or higher than the solar radiation part of this narrow SPECTRAL REGION in the brightness of above-mentioned sub-band fluorescent material radiation spectrum.Come from Y
2O
2The above-mentioned superiority of the fluorescent material of S:Eu is extensively verified and is proved in earth Different Climatic Zones time and again, this point has been discussed in No. 1004165 patents of MX that one of No. 2348943 patents of Canada CA that Bolchoukhine won and the contriver of this case Suo Xin N.P. is won, we with above-mentioned two patents as reference object of the present invention.
Although above-mentioned oxysulfide phosphor has as pointed superiority in the practice, yet they still have some substantial defectives, they are determined by following aspect, comprising coming from Y
2O
2The mass property of the fluorescent material of S:Eu, and the polymerization binding substances on the polyethylene basis is granular big dispersity material.
To point out these major defects below: 1. particulate loading is not high, is not more than 1.103 particulates/cm
2(plastic sheeting for farm use area), thereby decision polymerization plastic sheeting for farm use luminosity is not high; 2. cost is too high, makes area 1m usually
2Plastic sheeting for farm use consume the 150g polymeric material approximately; And 3. viewpoints according to us, these known plastic sheeting for farm use substantive defects interrelate with following reason, and are promptly excessive as the powder size of the employed fluorescent material of known plastic sheeting for farm use stopping composition, wherein powder mean sizes d
Cp=10～12 μ m, overall dimension is d
30～35 μ m.
Some experiments have been carried out by material synthetic specialty art breading, to get rid of known Y
2O
2This defective of S:Eu substrate fluorescent powder has been discussed desired raw material and half-finished dosing method in No. 1450358 patents of Russian SU that one of the contriver of this case Suo Xin N.P. is won.We are used this patent document as the prototype material, fluorescent material and plastic sheeting for farm use luminosity can be promoted 10～15% by this patent, and but effect is little yet significantly promote unit surface phosphor powder volumetric concentration.
Yet above-mentioned known technology is handled the defective of being discussed, and promptly not high the requirement in practice of the not high and relative light emission luminance value of plastic sheeting for farm use sulphur oxide phosphor powder volumetric concentration revised, and this is a main aim of the present invention.
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention is that a kind of red light fluorescent powder is provided, and it can make plastic sheeting for farm use sulphur oxide phosphor powder volumetric concentration improve and improve relative luminosity.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of red light fluorescent powder, and it not only has high radiation spectrum intensity, also has high-quantum efficiency, the short wave ultraviolet radiation can be converted to the red light radiation.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of red light fluorescent powder, and its powder mean sizes can be made a gesture of measuring with dark red optical wavelength in its ruddiness mutually with radiation.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of multilayer light conversion film, contains fine-grannular fluorescent material stopping composition in this multilayer light conversion film, and its characteristic is high photo bio effect, promotes crop yield.
For achieving the above object, the invention provides a kind of red light fluorescent powder, it is formed with the sulfide of strontium of rare earth element and/or hafnium and activator, it is characterized in that: above-mentioned materials is the fluorine oxysulfide of lanthanum-yttrium-zirconium and/or hafnium, and its total chemometric equation is: (La
1-x-y-zY
xA
yMe
z + 4O)
2S
1(F
-1)
2z, this activator comes from A=(TR
+ 3=∑ Eu, Sm, Gd, Tb)+(TR
+ 4=Pr
+ 4), in such cases, Me
+ 4=Zr
+ 4And/or Hf
+ 4
For achieving the above object, the invention provides a kind of multilayer light conversion film, it is to be used for greenhouse and hotbed, during forming, it is filled with fluorescent material and light is stablized component polymer, it is characterized in that: this multilayer light conversion film is made up of the light penetrating copolymer rete of same concentrations, this polymer system comes from new LDPE (film grade) and/or ethyl vinyl acetate, and be filled with phosphor powder, this fluorescent material is formed as mentioned above, in the case, its outside and middle part rete contain light conversion inorganic component, and its inner rete is added with the hard ester acid of machine and forms drop and fogging to prevent this film surface.
[embodiment]
At first, the objective of the invention is to eliminate the shortcoming of above-mentioned sulfur-bearing red light fluorescent powder.In order to reach this target, red light fluorescent powder of the present invention is formed with the sulfide and the activator of strontium of rare earth element and/or hafnium, and it is characterized in that: above-mentioned materials is the fluorine oxysulfide of lanthanum-yttrium-zirconium and/or hafnium, and its total chemometric equation is: (La
1-x-y-zY
xA
yMe
z + 4O)
2S
1(F
-1)
2z, this activator comes from A=(TR
+ 3=∑ Eu, Sm, Gd, Tb)+(TR
+ 4=Pr
+ 4), in such cases, Me
+ 4=Zr
+ 4And/or Hf
+ 4
Wherein, this chemometric equation (La
1-x-y-zY
xA
yMe
z + 4O)
2S
1(F
-1)
2zEach variable be respectively x=0.001～0.2; Y=0.01～0.2; Z=0.001～0.005.
Wherein, when ion concentration was 0.050＜Eu/ (Pr+Sm+Eu+Gd+Tb)≤0.15, the main radiation wavelength of this fluorescent material was positioned at range lambda=615～628nm.
Wherein, when ion concentration be 0.06＜(Eu+Sm)/Tr
+ 3≤ 0.095 o'clock, red radiation spectrum was positioned at the ultraviolet optical wavelength scope of λ=320～410nm in this fluorescent material.
Wherein, the mean sizes of this red light fluorescent powder powder is positioned at scope 0.4≤d
50≤ 0.8 μ m, this moment, the overall dimension of this powder was no more than d=6～8 μ m.
Below will briefly explain the essence that fluorescent material proposed by the invention is formed.Point out that at first fluorescent material proposed by the invention is different from the yttrium-europium oxysulfide phosphor of widespread use, it is lanthanum and yttrium oxysulfide sosoloid, also adds IV family element in the sosoloid, such as Zr
+ 4And/or Hf
+ 4This IV family element that adds is the basis of the hurried increase phenomenon of light-emitting phosphor brightness of the present invention, and the present invention adds small size La in fluorescent material is formed
+ 3And/or Y
+ 3, Zr
+ 4And/or Hf
+ 4, excited by the light in wavelength X=365～405nm zone.These element ions have higher electric charge and smaller szie, and substantive growth of crystal field power of the inner electrostatic field of this decision fluorine oxysulfide inorganic matrix causes that luminosity increases.
Secondly, come from trivalent element La in order to make
+ 3And Y
+ 3The tetravalence Zr of intracell
+ 4And/or Hf
+ 4The energy uniform distribution must add F in compound positively charged ion lattice is formed
-1On certain fluorine oxysulfide positively charged ion lattice node, the F that these added
-1Particular location also need precision more.Can infer F now
-1The internode position, also can be according to equation O
0 -2=F
i -1+ F
0 -1With the partial oxygen ion substitution they.As partial L a
+ 3Or Y
+ 3Substitute Zr
+ 4, the overall response formula is recorded as: (Zr
+ 4)=F
iOr (ZrY
+ 4)=(F
0 -1)+F
i -1
These reaction formula can also be explained, by adding the IV element (Zr of family
+ 4And/or Hf
+ 4), and internode F
-1 i, inner crystal field power increases in the fluorescent material matrix.
At last, for oxysulfide substrate fluorescent powder proposed by the invention, it can not only be by Eu
+ 3Activate, but also comprise Sm
+ 3, Gd
+ 3, Tb
+ 3The same with trivalent ion, can also use Pr in the fluorescent material matrix proposed by the invention
+ 4As activator and sensitizing agent, its characteristic shows as oxidisability+4-Pr
+ 4=Tr
+ 4These activator ion and compatible activator ions that add in the fluorine oxysulfide lattice composition also promote light-emitting phosphor brightness to increase.According to the data that is obtained, the growth pattern of light-emitting phosphor brightness is as follows: add La 1.
+ 3, brightness promotes 30-50%; 2. add F at internode
-1And as O
-2Substituting group, brightness promotes 10～20%; 3. add Zr
+ 4And/or Hf
+ 4Part substitutes La
+ 3Or Y
+ 3, brightness promotes 5～15%; And 4. add Pr
+ 4And Tb
+ 3Activator or sensitizing agent as a supplement, brightness promotes 25～30%.
Yttrium and lanthanum zirconium fluorine oxysulfide total brightness under europium, samarium, terbium and praseodymium activation increases by 90～140%.This substantive brightness growth is characterised in that, ionic concn ratio is 0.050＜Eu/ (Pr+Sm+Eu+Gd+Tb)≤0.15, the main wavelength of fluorescent material radiation is positioned at range lambda=615～628nm, at this moment replenishes the dark red zone of long-wave radiation spectrum that radiation just in time is positioned at wavelength X=705～715nm.Must be pointed out that this long-wave radiation can promote plant-growth (stem, root, leaf) and the communication switching of green plants synthetic tissue, also require the research of specialty about this point.
Substantive displacement takes place to the long wave direction of 390～410nm in fluorescent material photoluminescence laser spectrum proposed by the invention.Fluorescent material proposed by the invention is different from the fluorescent material of known type, this fluorescent material concentration content sum ∑ (Eu+Sm) and all rare-earth cation ∑ (Tr
+ 3) ratio range be 0.06＜(Eu+Sm)≤0.095, in this case, fluorescent material excites total spectrum to be positioned at the ultraviolet wavelength scope of λ=320～410nm.
Also must be pointed out an important feature of fluorescent material proposed by the invention, refer to that specifically the phosphor powder size can make a gesture of measuring in the optical wavelength of powder mutually with radiation.For phosphor powder proposed by the invention, its middle linear diameter is d
50=0.4～0.8 μ m can make a gesture of measuring in its optical wavelength mutually with radiation, wherein optical wavelength range lambda=62 8～715nm or average out to λ
0.65 μ m that is to say phosphor powder geometrical dimension d
50=0.6 μ m can make a gesture of measuring in its optical wavelength mutually with radiation.Point out that simultaneously the maximum center line value of phosphor powder is no more than d
Max=6～8 μ m.The present invention points out that once more (d compares with prototype
50=10～12 μ m), when phosphor powder size proposed by the invention taken place by substantive the growth, the novel material luminosity will increase to 1.8～2.4 times.Its reason of the substantive growth of fluorescent material brightness has been to create the new preparation process of the fluorine oxysulfide phosphor that comes from lanthanum-yttrium-europium-zirconium.
The various preparation methods of known rare earth element oxysulfide and/or oxyfluoride matrix embedded photoluminescent material, comprising, on the basis of these materials, carry out the pyroprocessing of initial yttrium-europium oxide compound (or oxalate) and free sulfur, wherein MeSn (n=5～10 down appear in free sulfur, Me=K or Na) in the compound of type, thermal treatment temp is 1100～1250 ℃.This process is carried out in closed alundum or carbon glass pot usually, and necessary reducing atmosphere guarantees the partial monosomy combustion of sulfur, promptly interacts with airborne oxygen.Need use hydrogen fluoride when adopting oxyfluoride to replace free sulfur among the preparation method, two fluoride amines are separated during thermolysis, and interact with original yttrium-europium oxide compound.Although this preparation scheme and products thereof is widely used, yet they still have some substantive defects: 1. the building-up process time length is 4 to 8 hours; 2. the consumption of sulfuration and/or fluorination reagent is big, and the stoichiometric number that is exceeded reaches 2.5-3 doubly; 3. synthetic carrying out in the process because the effect of alkaline product or fluorinated product, so crucible is corroded, the damage situation is serious.
The big dispersity of institute's synthetic materials is known oxysulfide phosphor preparation method's a very big defective.Because the powder size as the employed initial yttrium of raw material-europium oxide compound is d
50=4～6 μ m, thereby the phosphor powder minimum size is in this grade or more high-grade.The substantive growth can take place in powder size in the building-up process, reaches d usually
50=8～10 μ m.Big dispersity powder can destroy some critical natures of polymerization plastic sheeting for farm use, such as tensile strength and tensile strength.
For solving above-mentioned known oxysulfide phosphor preparation method's defective, the present invention also provides a kind of method for making of red light fluorescent powder, it comprises that rare earth element hydroxide and periodic system IV family element hydrogen oxide compound and sulfide and fluorochemical carry out heat shock response and the chemical coprecipitation that produces, it is characterized in that: this oxyhydroxide coprecipitation results from nitrate solution and/or the acetate solution, be positioned at temperature range T=200～900 ℃ with the thermal process reactor of sulfide and fluorochemical, this oxyhydroxide coprecipitation powder original dimensions is d
50=0.050～0.10 μ m.
Wherein, this oxyhydroxide coprecipitation results from the nitrate solution and/or acetate solution of hydrogen ion concentration pH＞2 in temperature about 80 ℃ and the medium.
Wherein, need use (NH as sulfide
2)
2CS, CH
3CSNH
2Or NH
4CNS, wherein the oxidisability of sulphur is-2, need use NH as fluorochemical this moment
4YF
2Or NH
4BF
4, in the case, the mass ratio of rare earth element hydroxide and sulfide and fluorochemical is 0.5: 2: 1～2: 2: 1.
Method proposed by the invention can be synthesized thin loosing and ultra-fine diffusing phosphor powder.The method for making of red light fluorescent powder proposed by the invention comprises that rare earth element hydroxide and periodic system IV family element hydrogen oxide compound and sulfide and fluorochemical carry out heat shock response, it is characterized in that, at first the above-mentioned element hydrogen oxide compound that comes from nitrate and/or acetate solution is carried out coprecipitation, temperature T
80 ℃, ℃ carry out in temperature range T=200～900 with the thermal process of postcure and fluorochemical response hydrogen ion concentration pH＞2 in the medium, and the original dimensions of oxyhydroxide coprecipitation powder is d
50=0.050～0.10 μ m.
Point out that at first preparation method Central Plains product proposed by the invention is generally oxyhydroxide, it is produced by initial nitric acid or acetic acid solution.When these solution interact oxyhydroxide is synthesized, contained essential substance concentration is 0.5～4m/L in the solution usually, hydrogen ion pH＞2 in the solution.The inventor finds in the course of the work, uses too much original solution acidic medium with the mass consumption original reagent, the compound of special lanthanum, at this moment pH＞5 and cause that the oxyhydroxide coprecipitation produces congregation.Need use concentrated ammonia solution (20%) as oxyhydroxide coprecipitation body, solution injects the response groove and carefully mixes with orthonitric acid solution.It is 75～80 ℃ that original solution has best precipitation temperature, and this is because higher temperature causes the unnecessary loss of initial material, oxyhydroxide can take place significantly condense when precipitation temperature is reduced to 40 ℃, the about 1 μ m of the agglomerate diameter that forms.
The analysis of coprecipitation product is pointed out, for example at (La
0.5Y
0.4Eu
0.09G
0.005Tb
0.005) (OH)
3.nH
2Lanthanum ion and ruthenium ion stoichiometric ratio were constant during O formed, and promptly the europium ion concentration ratio is [Eu]/[La+Y]=0.1, [La]/[Y]=1.25.Use traditional light settling process to be difficult to dispersion analysis is carried out in the oxyhydroxide coprecipitation.At this moment will use laser-diffractometer, it can accurately determine the powder of minimum size d=0.01 μ m.This instrument is such as but not limited to being analyser-2000 device of Germany " not Ritchie " company or the allied equipment of Chinese company.
The oxyhydroxide coprecipitation that the present invention is prepared is dry in oven heat, temperature be 150 ℃ to remove planar water.They are dazzling white product, and are compacted into bulk or sheet, the about 10mm of concentration, and they and sulfide or fluorochemical are levigate easily in drum grinder or mixer.These substantive superiority of oxysulfide phosphor preparation method proposed by the invention are not unique, it is characterized in that, use (NH as sulfidic material
2)
2CS, CH
3CSNH
2, NH
4CNS, wherein the oxidisability of sulphur equals-2, at this moment uses as fluorochemical to come from NH
4HF
2And/or NH
4BF
4The compound of ammonia, in this case, the mass ratio between rare earth element and IV family element and sulfide and the fluorochemical is 0.5: 4: 1～2: 4: 1.
Below will explain the essence of processing proposed by the invention.At first pointing out does not have IA family element positively charged ion fully in sulfide and the fluorochemical, these positively charged ions form when the thermal treatment of basic oxide (oxyhydroxide) melts, and cause the accelerated corrosion of crucible material, and promptly alundum or carbon glass are melted.Second variation that essential distinction is to vulcanize the reagent oxidation degree of technical finesse proposed by the invention.In known fluorine oxysulfide preparation method the oxidisability of employed free sulfur S or sulfurous gas be 0 or+4.Can draw from the constructive formula of these materials: the oxidisability of sulfuration reagent is-2 the preparation method proposed by the invention.
NH
2 -\ CH
3 -\
C＝S
-2 C＝S
-2 NH
4 +-SC＝-N
NH
2 -/ NH
2 -/
The very important characteristics that the present invention also points out these materials and had: they all have low melting point temperature, wherein for (NH
2)
2CS, T
Molten=168 ℃; CH
3CS-NH
2T
Molten=108.5 ℃; NH
4SCN T
Molten=149.5 ℃.This has illustrated following experimental fact, melts in the sulfide medium in first process stage generation sulfuration in the time of T=200 ℃.Determine S as the present invention
-2When the diffusion process of initial hydroxide surfaces transfer occurs in the material fusing, at this moment find diffusion deceleration phenomenon, its concrete manifestation is solid phase or gas-phase reaction.
The present invention points out simultaneously, forms H in the process of oxyhydroxide and sulfide decomposition reaction
2O, NH
4OH, CO
2Gaseous state type product, oxidizing atmosphere is converted to neutrality or weakly reducing atmosphere in the container of their promotion initial products.The sulfuration reagent in the building-up process and the decomposition course of fluorination reagent are closely similar.NH
4HF
2Decomposition reaction be: NH
4HF
2→ NH
3+ 2HF ↑, NH at this moment
4BF
4→ NH
3+ HF ↑+BF
3↑.
The present invention can determine best crucible charge framework by experiment, places oxyhydroxide coprecipitation and mixture of sulfides in the crucible, and both mass ratioes are 2: 4, and when wherein adding fluorochemical, three's mass ratio is 2: 4: 1.According to data of the present invention, in the 1000mL alundum crucible, place 400g rare earth element and IV family element hydrogen oxide compound, 400g sulfide.Batching is tightly compacted in crucible, and covers alundum mineral wool briquetting closely.Crucible setting is at the heating siege of silicon alloy (SiC) stove, and temperature remains in the stove:
2 ℃/minute of 20-100 ℃ of temperature rise rates
2 ℃/minute of 100-200 ℃ of temperature rise rates
4 ℃/minute of 200-400 ℃ of temperature rise rates
5 ℃/minute of 400-900 ℃ of temperature rise rates
900 ℃-kept 1 hour.About 5 hours of all heat treatment process time length, after this process furnace naturally cools to 80 ℃ with the crucible that is placed in wherein.The product that is loaded in the crucible is unloaded.Washing is carried out 3 times, and the final stage bath water should be acidified to PH=4.The prepared product response groove of packing into, very thin modification surface layer is coated on response groove middle-weight rare earths element and IV family element fluorine oxysulfide synthetic powder surface, and surface layer comes from the Si (OC of concentration 1%
2H
5)
4Nano level SiO after the solution hydrolysis
2Film.Subsequently the fluorescent material modified powder is carried out drying, T=120 ℃, the time length is 2 hours.At this moment phosphor powder obtains intensive ointment tone, and issues high light at the ultraviolet lamp of λ=365nm.The parameter testing of prepared fluorescent material need be used the spectrum photoelectric color comparator and the laser diffractometer of " Sensing " company, and simultaneously measured parameter is as shown in table 1.
Table 1
| Numbering | The fluorescent material chemical ingredients | Glow color | Tristimulus coordinates x y | Diameter center line μ m |
| 1 | (La 0,8Y 0,1Eu 0.08Gd 0.01Zr 0.005Pr 0.005O) 2S 1F 0.005 | Red λ=627nm | 0.635 0.358 | 0.6 |
| 2 | (La 0,8Y 0,08Eu 0.11Hf 0.005Tb 0.0 05Pr 0.005O) 2S 1F 0.01 | Red λ=628nm | 0.645 0.345 | 0.55 |
| 3 | (La 0,9Y 0,01Eu 0.08Zr 0.005Tb 0.00 1O) 2S 1F 0.02 | Red λ 1＝628nmλ 2＝708nm | 0.642 0.356 | 0.80 |
| 4 | (La 0,78Y 0,01Eu 0.19Zr 0.001Gd 0. 001O) 2S 1F 0.002 | Red λ=629nm λ=710nm | 0.655 0.344 | 0.44 |
| Numbering | The fluorescent material chemical ingredients | Glow color | Tristimulus coordinates x y | Diameter center line μ m |
| 5 | (La 0,7Y 0,05Eu 0.19Zr 0.010Zr 0.00 5O) 2S 1F 0.01 | Garnet λ=628nm λ=710nm | 0.658 0.340 | 0.65 |
| 6 | (La 0,7Y 0,05Eu 0.22Sm 0.02Gd 0.0 15Tb 0.01Zr 0.005O) 2S 1F 0.01 | Garnet λ=628nm λ=710nm | 0.654 0.344 | 0.6 |
| 7 | (La 0,6Y 0,2Eu 0.16Sm 0.01Gd 0.01 | Garnet | 0.640 | 0.75 |
| Tb 0.01Pr 0.005Hf 0.001O) 2S 1F 0.0 01 | λ＝628nm λ＝712nm | 0.352 | ||
| 8 | (La 0,7Y 0,2Eu 0.05Sm 0.01Gd 0.01Tb 0.01Pr 0.04Hf 0.005O) 2S 1F 0.00 1 | λ＝626nm λ＝710nm | 0.640 0.352 | 0.75 |
| 9 | Y 2O 2S:Eu 0.06Standard | λ＝616nm λ＝626nm | 0.640 0.346 | 0.80 |
In all inorganic fluorescent powder synthesized forms, the same with the parameter of being quoted in the table 1, also can determine their hydrolyte and light-stability.Carry out followingly determining that temperature is elevated to T=100 ℃ from T=80 ℃ for accelerated deterioration experiment, at λ=365nm, power density is 5W/cm
2Ultraviolet radiation under.Through being equivalent to the time of 2 months amount of exposures, substantial variation (less than 5%) does not take place in fluorescent material optical tech parameter.
The present invention also provides a kind of multilayer light conversion film in addition, it is to be used for greenhouse and hotbed, during forming, it is filled with fluorescent material and light is stablized component polymer, it is characterized in that: this multilayer light conversion film is made up of the light penetrating copolymer rete of same concentrations, this polymer system comes from new LDPE (film grade) (LDPE) and/or ethyl vinyl acetate (EVA), and be filled with phosphor powder, this fluorescent material is formed as mentioned above, in the case, its outside and middle part rete contain light conversion inorganic component, and its inner rete is added with the hard ester acid of machine and forms drop and fogging to prevent this film surface.
Wherein, the mass concentration of this fluorescent material is 0.1～0.5%.
Wherein, this light conversion inorganic component accounts for 0.2～0.6% of total mass.
Wherein, the concentration ratio of this polymer film is 1: 1: 1～1: 2: 1, and unit rete concentration is 20～50 μ m, and the rete total transmittancy is greater than 80%.
Wherein, the solar radiation short wavelength light of its convertible 180～250nm, quantum yield are 50～90%, promote in the green plants photo bio hormesis and output is promoted 35～70%.
Wherein, it can be converted to the sun short-wave radiation orange-red and emitting red light.
Multilayer light conversion film of the present invention (hereinafter to be referred as plastic sheeting for farm use) can be used for the modern optical conversion agricultural film of greenhouse and hotbed.The plastic sheeting for farm use that its fs creates has seemed out-of-date as individual layer cladding form.About known plastic sheeting for farm use, its structure defective comprises that concentration is big, and polymeric material (polyethylene) consumes big, and luminosity and web length have malconformation.Propose some perfect schemes for known plastic sheeting for farm use and manufacturing technology thereof among the present invention: 1. the present invention is made as three layers with plastic sheeting for farm use, and every layer denseer, more solid; 2. plastic sheeting for farm use is made by two stage process methods, uses the modern triple helical extrusion machine that is equipped with three feeding devices; 3. stratified film is through blowing and after adhesion contacts, and hurried cooling also is wrapped on the scroll bar under axial stress situation such as two-sided.
All three layers of plastic sheeting for farm uses compositions of the present invention have following characteristics: all add light inlet conversion phosphor powder in all three layers of plastic sheeting for farm uses, outer powder concn maximum of while, internal layer minimum 1.; 2. add photostabilizer at plastic sheeting for farm use in the outer and internal layer, prevent plastic sheeting for farm use in steam atmosphere owing to the solar ultraviolet intense radiation wrecks; 3. the plastic sheeting for farm use internal layer adds vehicle to strengthen the water stability on plastic sheeting for farm use surface, prevents condensation and the big water droplet that forms.Need use some stearate and derivative thereof as this water stablizer; 4. for multilayer agricultural film proposed by the invention, its main raw is a new LDPE (film grade), and density is ρ=0.91～0.92g/cm
3
The present invention also proposes, and plastic sheeting for farm use should be made the rete that becomes uniform concentration, and at this moment internal layer and outer concentration ratio are 1: 2.In order to strengthen plastic sheeting for farm use internal layer performance, add new LDPE (film grade) (LDPE) in the superconcentrate and come from the firm polymkeric substance (formation EVA) of ethyl vinyl acetate and it and polyethylene mixture.The present invention can determine that this matrix material is very firm, and price is only in costliness simultaneously, and wherein contained EVA and LDPE are no more than 20% of quality.Three layers of plastic sheeting for farm use total concn are 100 (internal layer 25 μ m, outer 25 μ m, middle level 50 μ m)～120 μ m (internal layer 30 μ m, outer 30 μ m, middle level 60 μ m) in this case.Three layers of plastic sheeting for farm use have following physics-mechanical parameter:
Table 2
| Numbering | Parameter | Sample 1 | Sample 2 | Sample 3 |
| 1 | Transverse tensile strength kg/cm 2 | 250 230 | 280 260 | 260 250 |
| 2 | Laterally extend relatively | 250 300 | 280 340 | 320 360 |
The reason that three layers of plastic sheeting for farm use has these high physics-mechanical parameters is that plastic sheeting for farm use proposed by the invention is in contact with one another by the identical light penetrating copolymer rete of firm concentration and forms, source of polymer is in new LDPE (film grade) and/or ethylethylene acetic ester, and be filled with fluorescent material, this fluorescent material is formed as mentioned above, its mass concentration is 0.1-0.5%, in this case, outside and middle part rete contains light conversion inorganic component, it accounts for the 0.2-0.6% of total mass, at this moment inner rete is added with the hard ester acid of machine, prevents that film surface from forming drop and fogging.The plastic sheeting for farm use surface can not form mist like this, thereby can keep light transmission for a long time.
For the light of radiation in multilayer agricultural film, the present invention has carried out spectral measurement.When plastic sheeting for farm use is subjected to when ultraviolet ray excited, the radioluminescence again that is produced can be divided into the ruddiness of λ=626～628nm and the dark red light of λ=708～710nm.The phosphor powder quantum yield was 50～90% during plastic sheeting for farm use was formed.Solar radiation medium ultraviolet linear light total points rate is about 6%, and photosynthetic to excite the increment of ruddiness be 3～5% to plastic sheeting for farm use like this, and this is enough for the Photosynthetic Response that stimulates green plants in greenhouse or the hotbed.Also must be pointed out an important feature of plastic sheeting for farm use proposed by the invention, promptly it has high luminosity.Compare with known plastic sheeting for farm use luminosity, the three layers of plastic sheeting for farm use that propose with novel ultra-fine diffusing fluorescent material are the former 2.5～4 times.
Different Climatic Zones in Russia, China and Korea S has been carried out the plastic sheeting for farm use spot testing.The research entity is the vegetables crop, as eggplant and capsicum etc." the big good fortune Buddhist nun of Cali " sweets capsicum ultimate production that Novosibirsk,Russia district summer in 2005 " Ao Bisike " is cultivated on the farm, greenhouse increases by 37%, and first vegetables sample is 10 days maturations in advance.From on August 28,12 days to 2005 July in 2005, the eggplant output that " Pusan " farm, greenhouse (Korea S) is cultivated promotes and reaches 56%, and the ripening stage shortens 17 days.In mid-September, 2005, the three layers of plastic sheeting for farm use in Jiangsu Province, China are applied to viticulture.Every string grape has full particle and mulberry, sweet, the succulence of taste, its increase of production 40%.Now, still continuing about the work of improving of three layers of plastic sheeting for farm use proposed by the invention.
In sum, red light fluorescent powder of the present invention and multilayer light conversion layer, it has: can make plastic sheeting for farm use sulphur oxide phosphor powder volumetric concentration improve and improve relative luminosity; It not only has high radiation spectrum intensity, also has high-quantum efficiency, the short wave ultraviolet radiation can be converted to the red light radiation; And the powder mean sizes can with radiation in its ruddiness make a gesture of measuring mutually with dark red optical wavelength and plastic sheeting for farm use in contain fine-grannular fluorescent material stopping composition, its characteristic is high photo bio effect, promote advantages such as crop yield, therefore, really can improve the shortcoming of known sulfur-bearing red light fluorescent powder and agricultural film.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to limit the present invention; anyly have the knack of this skill person, so protection scope of the present invention is when looking being as the criterion that the accompanying Claim book defined without departing from the spirit and scope of the present invention when can doing a little change and retouching.
Claims (9)
1. red light fluorescent powder, its sulfide and activator by hafnium is formed, and it is characterized in that: above-mentioned materials is the fluorine oxysulfide of lanthanum-yttrium-zirconium and hafnium, and its total chemometric equation is: (La
1-x-y-zY
xA
yMe
z 4+O)
2S
1(F
-1)
2z, x=0.001～0.2 wherein; Y=0.01～0.2; Z=0.001～0.005, this activator comes from A=(TR
3+=∑ Eu, Sm, Gd, Tb)+(TR
4+=Pr
4+), in the case, Me
4+=Zr
4+And Hf
4+
2. red light fluorescent powder as claimed in claim 1, wherein when ion concentration was 0.050＜Eu/ (Pr+Sm+Eu+Gd+Tb)≤0.15, the main radiation wavelength of this fluorescent material was positioned at range lambda=615～628nm.
3. red light fluorescent powder as claimed in claim 1, wherein the mean sizes of this red light fluorescent powder powder is positioned at scope 0.4≤d
50≤ 0.8 μ m, this moment, the overall dimension of this powder was no more than d=6 μ m.
4. the method for making of a red light fluorescent powder, it carries out the chemical coprecipitation that heat shock response produces for rare earth element hydroxide and periodic system IV family element hydrogen oxide compound and sulfide and fluorochemical, it is characterized in that: this oxyhydroxide coprecipitation results from nitrate solution and/or the acetate solution, be positioned at temperature range T=200～900 ℃ with the thermal response process of sulfide and fluorochemical, this oxyhydroxide coprecipitation powder original dimensions is d
50=0.050～0.10 μ m.
5. the method for making of red light fluorescent powder as claimed in claim 4 wherein need be used (NH as sulfide
2)
2CS, CH
3CSNH
2Or NH
4CNS, wherein the oxidisability of sulphur is-2, need use NH as fluorochemical this moment
4YF
2Or NH
4BF
4, in the case, the mass ratio of rare earth element hydroxide and sulfide and fluorochemical is 0.5: 2: 1～2: 2: 1.
6. multilayer light conversion film, it is used for greenhouse and hotbed, during forming, it is filled with fluorescent material and light is stablized component polymer, it is characterized in that: this multilayer light conversion film is made up of the light penetrating copolymer rete of same concentrations, and this source of polymer is in new LDPE (film grade) and/or ethyl vinyl acetate, and is filled with phosphor powder, this fluorescent material is formed according to claim 1, in the case, its outside and middle part rete contain light conversion inorganic component, and its inner rete is added with the hard ester acid of machine
To prevent that this film surface from forming drop and fogging
7. multilayer light conversion film as claimed in claim 6, wherein the mass concentration of this fluorescent material is 0.1～0.5%.
8. multilayer light conversion film as claimed in claim 6, wherein this light conversion inorganic component accounts for 0.2～0.6% of total mass.
9. multilayer light conversion film as claimed in claim 6, it can be converted to the sun short-wave radiation orange-red and emitting red light.
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| US8703015B2 (en) * | 2010-12-27 | 2014-04-22 | National Chiao Tung University | Yellow fluorosulfide phosphors for light-emitting diode and preparation method thereof |
| CN105315695B (en) * | 2015-10-29 | 2017-08-18 | 严梅霞 | A kind of agricultural film and its manufacture method |
| CN106316373A (en) * | 2016-07-29 | 2017-01-11 | 江苏罗化新材料有限公司 | Preparing method for high power illuminant fluoride florescent and crystalline ceramics |
| CN110698811B (en) * | 2019-09-04 | 2022-08-05 | 深圳嘉会生物科技有限公司 | Light conversion film capable of promoting plant growth and preparation method and application thereof |
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