CN109135746A - A kind of environment-friendly type fluorescent powder - Google Patents
A kind of environment-friendly type fluorescent powder Download PDFInfo
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- CN109135746A CN109135746A CN201811168764.6A CN201811168764A CN109135746A CN 109135746 A CN109135746 A CN 109135746A CN 201811168764 A CN201811168764 A CN 201811168764A CN 109135746 A CN109135746 A CN 109135746A
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- 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
- C09K11/7767—Chalcogenides
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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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
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
Abstract
The present invention relates to lighting area, a kind of environment-friendly type fluorescent powder and preparation method thereof is provided, for reducing larger problem is polluted in fluorescent powder production process.A kind of environment-friendly type fluorescent powder provided by the invention, including fluorescent powder and calcium carbonate, 1 ~ 3 mass parts of fluorescent powder, 2 ~ 40 mass parts of calcium carbonate.Fluorescent powder is mixed with calcium carbonate according to certain proportion, can significantly improve the dispersibility of fluorescent powder, while the optical homogeneity of fluorescent powder has significant raising；Production technology is relatively simple, and whole process waste is few, more friendly to environment.
Description
Technical field
The present invention relates to lighting areas, and in particular to a kind of environment-friendly type fluorescent powder.
Background technique
YAG-Ce fluorescent powder is a kind of luminescent material that must be used in white light LED part.It is manufactured with burning synthesis method
YAG-Ce fluorescent powder can be such that synthesis reaction temperature is greatly lowered, and significantly save electric power, and will lead to cost decline.In electricity
Power today in short supply and at high cost, the technology of energy-saving and environmental protection are even more important.Existing white light LEDs YAG-Ce fluorescent powder
Manufacturing method be essentially all traditional high temperature solid-state method (or its modification method), reaction temperature is high, is not less than mostly
1400 DEG C (general 1400-1700 DEG C).According to reaction raw materials type, the difference of particle variation, pre-treatment, reaction temperature is had centainly
Difference, but overall all high, energy consumption, not environmentally.
The white light LEDs being widely used are made up of blue LED die and yellow fluorescent powder.In LED encapsulation, usually
Fluorescent powder is mixed into silica gel or epoxide-resin glue, in re-coating to chip, since phosphor's density is greater than silica gel and asphalt mixtures modified by epoxy resin
, there is fluorescent powder deposited phenomenon in dispensing and solidification process in rouge glue density.Deposited phenomenon will lead to fluorescent powder and be unevenly distributed,
Luminous efficiency is reduced, influences LED color uniformity and optical homogeneity, so that the yields of LED is lower, bring is direct
Consequence is the cost for increasing user and using LED product.
Summary of the invention
Present invention solves the technical problem that polluting larger problem to reduce in fluorescent powder production process, a kind of environmental protection is provided
Type fluorescent powder.
In order to solve the above technical problem, the present invention provides technical solution are as follows:
A kind of environment-friendly type fluorescent powder, including fluorescent powder and calcium carbonate, 1 ~ 3 mass parts of fluorescent powder, the calcium carbonate 2 ~
40 mass parts.
Fluorescent powder is mixed with calcium carbonate according to certain proportion, can significantly improve the dispersibility of fluorescent powder, while glimmering
The optical homogeneity of light powder has significant raising.
Production technology is relatively simple, and whole process waste is few, more friendly to environment.
Preferably, the fluorescent powder is YAG-Ce fluorescent powder；The fluorescent powder includes 530 ~ 710 mass of aluminium oxide
Part, 215 ~ 395 mass parts of yttrium oxide, 2 ~ 21 mass parts of cerium oxide.YAG fluorescent powder is the main glimmering of industrialized production white light LED
Light powder, YAG are excited and issue yellow light and remaining blue light forms white light, and White light LED technology is for reasonable energy utilization, slow
Solution energy crisis and green illumination are of great significance.
Preferably, the fluorescent powder includes 630 mass parts of aluminium oxide, 285 mass parts of yttrium oxide, 5 mass parts of cerium oxide.
The uniformity of the fluorescent powder configured within this range is more preferable, and material utilization is higher, can produce better optical homogeneity.
Preferably, the fluorescent powder is made by the following method: taking 270 ~ 310 mass parts of incendiary agent, same to aluminium oxide, oxygen
It is heated after changing yttrium, cerium oxide mixing, ball milling；In the heating process, 320 ~ 650 DEG C are first warming up to, then is warming up to 1050 DEG C,
3 ~ 4h is reacted at this temperature, is gradually decrease to room temperature, is obtained intermediate powder, the intermediate powder obtains after ball milling
YAG-Ce fluorescent powder.Fluorescent powder is manufactured using combustion method, reaction temperature can be effectively reduced, reach and close at a lower temperature
At the effect of fluorescent powder, energy cost declines to a great extent, and the environment protecting of the technological process of production further increases.
Preferably, the incendiary agent is the mixture of urea, oxalic acid, ethylene glycol.Fuel, Ke Yijin are in organic combustion agent
One step reduces reaction required temperature, and then reduces energy consumption, while also can guarantee the illumination effect of fluorescent powder.
Preferably, the calcium carbonate is modified calcium carbonate, and the modified calcium carbonate is made by the following method: will receive
After 10 ~ 15 mass parts of rice calcium carbonate are with the deionized water mixing of 1200 ~ 1400 mass parts, the hydrogen-oxygen of 0.1 ~ 0.2 mass parts is added
Change sodium, stirs to being completely dissolved, obtain suspension slurry；Obtained suspension slurry is heated, maintaining heating temperature is 80 ~ 90 DEG C, is added
Thermal process, which summarizes, to be kept stirring；After heating 2h, 0.5 ~ 0.7 mass parts of lauric acid are added, continues 1 ~ 3h of stirring, filters to take filter residue,
Ball milling obtains modified nano calcium carbonate after drying.Calcium carbonate can wrap up fluorescent powder grain, further increase the dispersion of fluorescent powder
Property；But the illumination effect for the fluorescent powder that calcium carbonate directly wraps up is declined, therefore, after being modified to calcium carbonate, Ke Yi
On the basis of the dispersibility for improving fluorescent powder, the illumination effect of fluorescent powder is improved.
Preferably, the modified calcium carbonate is made by the following method: by 12 mass parts of nanometer calcium carbonate with 1250 matter
After the deionized water mixing for measuring part, the sodium hydroxide of 0.15 mass parts is added, stirs to being completely dissolved, obtains suspension slurry；Add
The suspension slurry that heat obtains, maintaining heating temperature is 85 DEG C, and heating process, which summarizes, to be kept stirring；After heating 2h, lauric acid is added
0.6 mass parts continue to stir 2h, filter to take filter residue, ball milling obtains modified nano calcium carbonate after drying.Herein preferably formula and
Under manufacture craft, the illumination effect of fluorescent powder is further increased, and dispersion performance is also obviously improved.
Preferably, the drying is at 100 ~ 120 DEG C, and the drying carries out under the air draught of flowing.Carbonic acid
The drying temperature of calcium is unsuitable excessively high, otherwise will lead to Decomposition of Calcium Carbonate, reduces the dispersion effect of fluorescent powder.
A kind of preparation method of environment-friendly type fluorescent powder, comprising: after fluorescent powder is mixed with vector resin, then it is mixed with calcium carbonate
It closes, after mixing, obtains mixing aggregate；Aggregate rotation is smashed, 3000 ~ 5000r/min of revolving speed, it is mixed after smashing
It closes object and obtains environment-friendly type fluorescent powder after airflow screening.Fluorescent powder is combined together by resin with calcium carbonate, by high speed
The powder that rotation obtains after smashing can be effectively dispersed in epoxy resin, improve the illumination effect of LED.
Preferably, the vector resin is the mixture of amine resin and polyacrylic resin, is beaten for the rotation
Revolving speed during broken is 4000r/min.Amine resin is 1:1 ~ 1:2 with the ratio of polyacrylic resin in mixture.
Compared with prior art, the device have the advantages that are as follows: fluorescent powder is mixed according to certain proportion with calcium carbonate
It closes, can significantly improve the dispersibility of fluorescent powder, while the optical homogeneity of fluorescent powder has significant raising；Production technology
Relatively simple, whole process waste is few, more friendly to environment.
The application is optimized from the formula of production and technique, while ensure that the quality of production of fluorescent powder, is reduced
The discharge of pollutant, only prepares the process of fluorescent powder in combustion method in production process, has a small amount of exhaust gas to generate, but the part is useless
Gas can be processed in turn by abundant collection, therefore small pollution of the environment, is a kind of fluorescent powder of environment-friendly type.
Specific embodiment
Following implementation column is to further explanation of the invention, is not limitation of the present invention.
Embodiment 1
A kind of environment-friendly type fluorescent powder, including fluorescent powder and calcium carbonate, 2 mass parts of fluorescent powder, 25 matter of calcium carbonate
Measure part.The fluorescent powder includes 630 mass parts of aluminium oxide, 285 mass parts of yttrium oxide, 5 mass parts of cerium oxide.The fluorescence
Powder is made by the following method: taking 300 mass parts of incendiary agent, heats after same aluminium oxide, yttrium oxide, cerium oxide mixing, ball milling；Institute
In the heating process stated, 450 DEG C are first warming up to, then is warming up to 1050 DEG C, 3.5h is reacted at this temperature, is gradually decrease to room
Temperature, obtains intermediate powder, and the intermediate powder obtains YAG-Ce fluorescent powder after ball milling.The incendiary agent be urea,
The mixture of oxalic acid, ethylene glycol.The modified calcium carbonate is made by the following method: 12 mass parts of nanometer calcium carbonate are same
After the deionized water mixing of 1250 mass parts, the sodium hydroxide of 0.15 mass parts is added, stirs to being completely dissolved, obtains the slurry that suspends
Liquid；Obtained suspension slurry is heated, maintaining heating temperature is 85 DEG C, and heating process, which summarizes, to be kept stirring；After heating 2h, the moon is added
0.6 mass parts of cinnamic acid continue to stir 2h, filter to take filter residue, ball milling obtains modified nano calcium carbonate after drying.The drying is
At 110 DEG C, the drying carries out under the air draught of flowing.
Fluorescent powder is mixed with calcium carbonate according to certain proportion, can significantly improve the dispersibility of fluorescent powder, while glimmering
The optical homogeneity of light powder has significant raising.
Production technology is relatively simple, and whole process waste is few, more friendly to environment.YAG fluorescent powder is industrial metaplasia
The major fluorescent powder of white light LEDs is produced, YAG is excited and issues yellow light and remaining blue light formation white light, White light LED technology pair
It is of great significance in reasonable energy utilization, alleviating energy crisis and green illumination.It adds in above-mentioned material and is configured in range
The uniformity of fluorescent powder is more preferable, and material utilization is higher, can produce better optical homogeneity.Fluorescence is manufactured using combustion method
Powder can effectively reduce reaction temperature, achieve the effect that synthetizing phosphor powder at a lower temperature, energy cost substantially under
Drop, the environment protecting of the technological process of production further increase.Fuel is done in organic combustion agent, can further decrease temperature needed for reaction
Degree, and then energy consumption is reduced, while also can guarantee the illumination effect of fluorescent powder.Calcium carbonate can wrap up fluorescent powder grain, into
The dispersibility of one step raising fluorescent powder；But the illumination effect for the fluorescent powder that calcium carbonate directly wraps up is declined, therefore, to carbonic acid
After calcium is modified, the illumination effect of fluorescent powder can be improved on the basis of improving the dispersibility of fluorescent powder.Calcium carbonate is done
Dry temperature is unsuitable excessively high, otherwise will lead to Decomposition of Calcium Carbonate, reduces the dispersion effect of fluorescent powder.
A kind of preparation method of environment-friendly type fluorescent powder, comprising: after fluorescent powder is mixed with vector resin, then it is mixed with calcium carbonate
It closes, after mixing, obtains mixing aggregate；Aggregate rotation is smashed, by the mixture after smashing after airflow screening
Obtain environment-friendly type fluorescent powder.The vector resin is the mixture of amine resin and polyacrylic resin, is the rotation
Revolving speed during smashing is 4000r/min.
Fluorescent powder is combined together by resin with calcium carbonate, and the powder obtained after high speed rotation is smashed can be effective
Dispersion in the epoxy, improve the illumination effect of LED.Amine resin is 1 with the ratio of polyacrylic resin in mixture:
1。
Embodiment 2
Embodiment 2 with embodiment 1 the difference is that, including fluorescent powder and calcium carbonate, 1 mass parts of fluorescent powder are described
2 mass parts of calcium carbonate.The fluorescent powder is YAG-Ce fluorescent powder；The fluorescent powder includes 530 mass parts of aluminium oxide, oxygen
Change 215 mass parts of yttrium, 2 ~ 21 mass parts of cerium oxide.The fluorescent powder is made by the following method: taking 270 mass of incendiary agent
Part, it is heated after same aluminium oxide, yttrium oxide, cerium oxide mixing, ball milling；In the heating process, 320 DEG C are first warming up to, then rise
Temperature reacts 3h at this temperature, is gradually decrease to room temperature to 1050 DEG C, obtains intermediate powder, and the intermediate powder passes through ball
YAG-Ce fluorescent powder is obtained after mill.The incendiary agent is the mixture of urea, oxalic acid, ethylene glycol.The calcium carbonate is to change
Property calcium carbonate, the modified calcium carbonate is made by the following method: by 10 mass parts of nanometer calcium carbonate with 1200 mass parts
After deionized water mixing, the sodium hydroxide of 0.1 mass parts is added, stirs to being completely dissolved, obtains suspension slurry；What heating obtained
Suspension slurry, maintaining heating temperature is 80 DEG C, and heating process, which summarizes, to be kept stirring；After heating 2h, 0.5 mass of lauric acid is added
Part, continue stirring 1, filters to take filter residue, ball milling obtains modified nano calcium carbonate after drying.The drying be at 100 DEG C, it is described
Drying carried out under the air draught of flowing.
Embodiment 3
Embodiment 3 with embodiment 1 the difference is that, including fluorescent powder and calcium carbonate, 3 mass parts of fluorescent powder are described
40 mass parts of calcium carbonate.The fluorescent powder is YAG-Ce fluorescent powder；The fluorescent powder includes 710 mass parts of aluminium oxide,
395 mass parts of yttrium oxide, 21 mass parts of cerium oxide.The fluorescent powder is made by the following method: taking 310 mass of incendiary agent
Part, it is heated after same aluminium oxide, yttrium oxide, cerium oxide mixing, ball milling；In the heating process, 650 DEG C are first warming up to, then rise
Temperature reacts 4h at this temperature, is gradually decrease to room temperature to 1050 DEG C, obtains intermediate powder, and the intermediate powder passes through ball
YAG-Ce fluorescent powder is obtained after mill.The incendiary agent is the mixture of urea, oxalic acid, ethylene glycol.The calcium carbonate is to change
Property calcium carbonate, the modified calcium carbonate is made by the following method: by 15 mass parts of nanometer calcium carbonate with 1400 mass parts
After deionized water mixing, the sodium hydroxide of 0.2 mass parts is added, stirs to being completely dissolved, obtains suspension slurry；What heating obtained
Suspension slurry, maintaining heating temperature is 90 DEG C, and heating process, which summarizes, to be kept stirring；After heating 2h, 0.7 mass of lauric acid is added
Part, continue to stir 3h, filters to take filter residue, ball milling obtains modified nano calcium carbonate after drying.The drying is the institute at 120 DEG C
The drying stated carries out under the air draught of flowing.
Embodiment 4
Embodiment 4 with embodiment 1 the difference is that, the preparation method include: by fluorescent powder with vector resin mix after,
It is mixed again with calcium carbonate, after mixing, obtains mixing aggregate；Aggregate rotation is smashed, revolving speed 3000r/min will be beaten
Mixture after broken obtains environment-friendly type fluorescent powder after airflow screening.
Embodiment 5
Embodiment 5 with embodiment 1 the difference is that, comprising: after fluorescent powder is mixed with vector resin, then mixed with calcium carbonate
It closes, after mixing, obtains mixing aggregate；Aggregate rotation is smashed, revolving speed 5000r/min, by the mixture after smashing
Environment-friendly type fluorescent powder is obtained after airflow screening.
Embodiment 6
Embodiment 6 with embodiment 1 the difference is that, the calcium carbonate is unmodified.
Comparative example 1
Comparative example 1 with embodiment 1 the difference is that, contain only fluorescent powder in the environment-friendly type fluorescent powder, not calcium carbonate.
Comparative example 2
Comparative example 2 with embodiment 1 the difference is that, in the environment-friendly type fluorescent powder include 0.5 mass parts of fluorescent powder, carbonic acid
2 mass parts of calcium.
Comparative example 3
Comparative example 3 with embodiment 1 the difference is that, in the environment-friendly type fluorescent powder include 4 mass parts of fluorescent powder, calcium carbonate
50 mass parts.
Comparative example 4
Comparative example 4 with embodiment 1 the difference is that, in the environment-friendly type fluorescent powder include 0.5 mass parts of fluorescent powder, carbonic acid
50 mass parts of calcium.
Comparative example 5
Comparative example 5 with embodiment 1 the difference is that, in the environment-friendly type fluorescent powder include 4 mass parts of fluorescent powder, calcium carbonate
2 mass parts.
Experimental example
By analysis embodiment 1 ~ 6 and comparative example 1 ~ 5 fluorescent powder packaging into lamps and lanterns, measure at all they relative luminance and
Dispersion performance carries out formula and preparation process preferred.
As can be known from the above table, the capable of emitting normal white light of embodiment 1 ~ 5, but the light in embodiment 4 slightly has non-uniform phenomenon
Occur, the revolving speed that stirring when this may be crushed with it crushes is smaller related.But brightness and the hair for the fluorescent powder that embodiment is related to
The color of light is all satisfied requirement, shows that brightness and the illumination effect of fluorescent powder can be improved in the formula of the application and preparation method.
Relative luminance highest in embodiment 1, shows under preferred technological parameter and material dosage, the production of the application
The available further raising of the performance parameter of product；Brightness in embodiment 2 and 3 is lower, may produce with its fluorescent powder
The dosage of various oxides in journey is excessive or very few related, but to be all satisfied color normal for the illumination effect in embodiment 1 ~ 3
Shine excellent requirement.
In embodiment 4 and 5, the technological parameter when mixing of calcium carbonate and fluorescent powder is changed, the light in embodiment 4
It is more uneven, after showing that calcium carbonate and fluorescent powder compound in the application, in the two mixed process, it is necessary to adequately crush.
In embodiment 6, calcium carbonate is unmodified, and relative luminance is markedly less than embodiment 1 ~ 5, shows the calcium carbonate in the application
The modified luminescent properties that can effectively improve fluorescent powder.
Be not added with calcium carbonate in comparative example 1, the dispersion effect of fluorescent powder is poor, illumination effect and brightness it is significant under
Drop.
In comparative example 2 ~ 5, calcium carbonate is different with the proportion of fluorescent powder, it can be seen that its illumination effect, which is significantly lower than, to be implemented
Example 1 ~ 6 shows adequately improve illumination effect and bright under the dosage of fluorescent powder and calcium carbonate that the application determines
Degree.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and above embodiments are not to limit this
The scope of the patents of invention, all equivalence enforcements or change without departing from carried out by the present invention, is intended to be limited solely by the scope of the patents of this case.
Claims (10)
1. a kind of environment-friendly type fluorescent powder, which is characterized in that including fluorescent powder and calcium carbonate, 1 ~ 3 mass parts of fluorescent powder, institute
2 ~ 40 mass parts of calcium carbonate stated.
2. a kind of environment-friendly type fluorescent powder according to claim 1, which is characterized in that the fluorescent powder is YAG-Ce fluorescence
Powder；The fluorescent powder includes 530 ~ 710 mass parts of aluminium oxide, 215 ~ 395 mass parts of yttrium oxide, 2 ~ 21 mass parts of cerium oxide.
3. a kind of environment-friendly type fluorescent powder according to claim 2, which is characterized in that the fluorescent powder includes aluminium oxide
630 mass parts, 285 mass parts of yttrium oxide, 5 mass parts of cerium oxide.
4. a kind of environment-friendly type fluorescent powder according to claim 2, which is characterized in that the fluorescent powder is by the following method
It is made:
270 ~ 310 mass parts of incendiary agent are taken, are heated after same aluminium oxide, yttrium oxide, cerium oxide mixing, ball milling；
In the heating process, 320 ~ 650 DEG C are first warming up to, then is warming up to 1050 DEG C, reacts 3 ~ 4h at this temperature, gradually
It is reduced to room temperature, obtains intermediate powder, the intermediate powder obtains YAG-Ce fluorescent powder after ball milling.
5. a kind of environment-friendly type fluorescent powder according to claim 4, which is characterized in that the incendiary agent be urea, oxalic acid,
The mixture of ethylene glycol.
6. a kind of environment-friendly type fluorescent powder according to claim 1, which is characterized in that the calcium carbonate is modified carbonic acid
Calcium, the modified calcium carbonate are made by the following method:
After 10 ~ 15 mass parts of nanometer calcium carbonate are mixed with the deionized water of 1200 ~ 1400 mass parts, 0.1 ~ 0.2 mass is added
The sodium hydroxide of part stirs to being completely dissolved, obtains suspension slurry；
Obtained suspension slurry is heated, maintaining heating temperature is 80 ~ 90 DEG C, and heating process, which summarizes, to be kept stirring；
After heating 2h, 0.5 ~ 0.7 mass parts of lauric acid are added, continue 1 ~ 3h of stirring, filters to take filter residue, ball milling is changed after drying
Property nanometer calcium carbonate.
7. a kind of environment-friendly type fluorescent powder according to claim 6, which is characterized in that the modified calcium carbonate passes through following
Method is made:
After 12 mass parts of nanometer calcium carbonate are mixed with the deionized water of 1250 mass parts, the hydroxide of 0.15 mass parts is added
Sodium stirs to being completely dissolved, obtains suspension slurry；
Obtained suspension slurry is heated, maintaining heating temperature is 85 DEG C, and heating process, which summarizes, to be kept stirring；
After heating 2h, 0.6 mass parts of lauric acid are added, continue to stir 2h, filter to take filter residue, ball milling obtains modified Nano after drying
Calcium carbonate.
8. a kind of environment-friendly type fluorescent powder according to claim 1, which is characterized in that the drying be at 100 ~ 120 DEG C,
The drying carries out under the air draught of flowing.
9. a kind of preparation method of environment-friendly type fluorescent powder characterized by comprising
After fluorescent powder is mixed with vector resin, then with calcium carbonate mixing, after mixing, mixing aggregate is obtained；
Aggregate rotation is smashed, the mixture after smashing is obtained ring by 3000 ~ 5000r/min of revolving speed after airflow screening
Guarantor's type fluorescent powder.
10. a kind of preparation method of environment-friendly type fluorescent powder according to claim 9, which is characterized in that the carrier tree
Rouge is the mixture of amine resin and polyacrylic resin, and the revolving speed during smashing for the rotation is 4000r/min.
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| CN110499665A (en) * | 2019-08-13 | 2019-11-26 | 湖南省南盾防伪技术实业有限公司 | Calcium carbonate wraps up DNA- fluorescent dye composite Nano gel Double anti-counterfeit preparation method for coating |
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| CN103862760A (en) * | 2014-03-28 | 2014-06-18 | 裴晓迪 | Light-emitting plate and manufacturing method thereof |
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