CN105419309A - Preparation method of luminescent polyamide composite material - Google Patents
Preparation method of luminescent polyamide composite material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—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
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention discloses a preparation method of a luminescent polyamide composite material. The method comprises the following steps of (1) preparing a graphene/red-light phosphor/SiO2 composite material; (2) weighing the following materials in parts by weight: 60 to 70 parts of nylon resin, 30 to 40 parts of hybrid glass fiber reinforcement, 1 to 5 parts of nylon master batch, 1 to 5 parts of graphene/red-light phosphor composite material and 0.1 to 0.3 part of antioxygen; extruding the materials by a double-screw extruder and pelleting, wherein the hybrid glass fiber reinforcement is added through a side-feeder, the screw speed of the double-screw extruder is 120 to 150r/min, the temperature is 265 to 280 DEG C, and then the polyamide composite material is obtained. The preparation method of the luminescent polyamide composite material can enhance the dispersity and the luminance uniformity of phosphor in the luminescent polyamide composite material, and the high luminescent intensity is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of luminous polyamide matrix material.
Background technology
Nylon is as the engineering plastics that output is maximum in the world, range of application is the widest, and it is high that it has mechanical strength; Excellent self lubricity and wear resistance; Wearability, chemical proofing; Processing characteristics is excellent, is easy to the advantages such as machine-shaping.Be widely used in automotive industry, the field such as electric, mechanical.
Graphene (Graphene) is the allotropic substance that the carbon of discovered in recent years is new, have by carbon atom with the individual layer Two-dimensional Carbon material of sp2 hybridized orbital bonding, its basic structural unit is benzene six-ring the most stable in organic materials, is material the thinnest in the world at present.Graphene is due to its typical two-dirnentional structure, there is excellent electric property (room temperature electron mobility can reach 200000cm2V-1S-1), thermal property (thermal conductivity reaches 5000Wm-1K-1), (Young's modulus is 1100GPa to mechanical property, breaking tenacity is 125GPa), and special quantum hall effect and quantum tunneling effect etc.Owing to possessing above-mentioned various performance, Graphene has broad application prospects in field of compound material, obtains the extensive research of lot of domestic and foreign scholar.
But be applied on nylon material by Graphene at present, the polymer-modified effect of independent Graphene is undesirable, makes the application of Graphene on nylon material be restricted.When needing acquisition to have the nylon material of luminescent properties, generally fluorescent material is mixed with nylon material extrude processing, but due to the bad dispersibility of fluorescent material in resin composite materials, easy generation agglomeration, uniformity of luminance is poor, and luminous intensity is more weak, luminescent properties and/or twilight sunset effect also can be lost seriously, are unfavorable for the application of luminous nylon material.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation method of luminous polyamide matrix material, strengthening the dispersiveness of fluorescent material in polyamide compoiste material and uniformity of luminance, and there is high luminous intensity.
Technical problem to be solved by this invention is achieved by the following technical programs:
A preparation method for luminous polyamide matrix material, comprises the following steps:
(1) prepare Graphene/red light fluorescent powder matrix material: added by 1g Graphene in 100ml deionized water, under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; By 25 ~ 100gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip red light fluorescent powder dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic;
(2) Graphene/red light fluorescent powder/SiO is prepared
2matrix material: 0.5g Graphene/red light fluorescent powder matrix material is scattered in ethanol under 300 ~ 500KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir; Add a certain proportion of water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/red light fluorescent powder matrix material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; This is coated with SiO
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; This mixture is immersed in ultrasonic 5 ~ 60min in hydrofluoric acid, removes the silicon-dioxide of part, centrifugal and dry, obtain Graphene/Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06fluorescent material/SiO
2matrix material;
(3) material is taken by following portions by weight: nylon resin 60 ~ 70 parts, mix glass fiber reinforcements 30 ~ 40 parts, nylon master batch 1 ~ 5 part, Graphene/1 ~ 5 part, red light fluorescent powder matrix material and 0.1 ~ 0.3 part, oxidation inhibitor; Extruded and granulation through twin screw extruder by above-mentioned material, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 120 ~ 150r/min, and temperature is 265 ~ 280 DEG C, namely obtains polyamide compoiste material.
The present invention has following beneficial effect: the preparation method of this luminous polyamide matrix material, and it strengthens the dispersiveness of fluorescent material in polyamide compoiste material and uniformity of luminance, and has high luminous intensity.
Embodiment
In the present invention,
(1) Graphene is obtained by following methods: get a certain amount of sour flat band ink, 1000 DEG C process 1 hour, then at 7%H in atmosphere
2nitrogen and hydrogen mixture in 1000 DEG C of in-situ reducing process 1.5 hours, add the macrogol ester of mass ratio 3% and tetracarboxylic dianhydride's dinaphthyl of mass ratio 5.0% again, the slurry that concentration is 80.0% is made into water, first under power is the ultrasonic assistant of 400W, carry out 3500 revs/min of ball millings 8 hours, 2000 revs/min of ball millings are carried out 4 hours under being adjusted to 200W ultrasonic wave again, through supercentrifuge 10000 revs/min separation after ball milling, lyophilize, obtains Graphene solid.
(2) quantum dot calcium carbonate, its preparation method can prepare the method for nano calcium carbonate quantum dot with reference to a kind of microemulsion system disclosed in Chinese patent CN103570051B, specifically first prepare the nano-calcium carbonate microemulsion of 1 ~ 3nm, then through rotary evaporation also dry obtained quantum dot calcium carbonate powders.
(3) preparation method of nano-kaoline is as follows: by 150g kaolin ore with the rotating speed ball milling 60 minutes of 1500 revs/min, then insert in 5L deionized water, add 220g Potassium ethanoate and stir 60 minutes, suction filtration cleaning is about 7 to pH value, then with the rotating speed ball milling 60 minutes of 1200 revs/min after drying under 80 degree of conditions, carry out 1800 revs/min of ball millings under being adjusted to 300W ultrasonic wave again 1 hour, obtain the kaolin powder of particle diameter at 10 ~ 30nm.
(4) Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano fluorescent powder, preparation method thereof is as follows: (a) is by 2.4mmolNAVO
412H
2o is dissolved in the mixing solutions containing 10ml ethylene glycol and 3ml distilled water; B above-mentioned solution 300r/min centrifugal speed is stirred below the dropwise Y (NO of instillation containing the certain proportioning of 2.7mmol by ()
3)
36H
2o, Eu (NO
3)
3, Al (NO
3)
3(0.9:0.04:0.06) in 12ml ethylene glycol solution, then clarify to solution at 500r/min centrifugal speed stirring 5 ~ 10min, add 15ml distilled water; C reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml by (), under vacuum conditions, and 170
oinsulation reaction 90min under C, after reaction terminates, is quickly cooled to room temperature; Gained suspension is poured out, centrifugal and obtain white precipitates by acetone and washed with de-ionized water 3 times successively; D this is deposited in 90 by ()
ounder C, dry 4h, obtains nano-phosphor; E nano-phosphor ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir) is scattered in ethanol by (); Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and nano-phosphor after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 6 hours; Carry out centrifugal and obtain white precipitate 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell nano fluorescent material; F this is coated with SiO by ()
2core-shell nano fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; G fluorescent material mixture is immersed in ultrasonic 1h in hydrofluoric acid by (), remove silicon-dioxide, centrifugal and dry, obtains the Y of median size 10 ~ 20nm
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor.
(5) graphene/carbon acid calcium compounded mix, Graphene/kaolin compounded mix, Graphene/red light fluorescent powder matrix material, Graphene/long-afterglow fluorescent powder composite material is prepared:
The preparation method of graphene/carbon acid calcium compounded mix is as follows: added by 1g Graphene in 100ml deionized water, under 800 ~ 1000kW ultrasonic vibration and 500 ~ 1000r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; Add in 500ml deionized water by 100g quantum dot calcium carbonate, under 1200 ~ 1500kW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir, dispersion obtained calcium carbonate dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip calcium carbonate dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained graphene/carbon acid calcium compounded mix down 100kW is ultrasonic.
The preparation method of Graphene/kaolin compounded mix is as follows: added by 1g Graphene in 100ml deionized water, and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; Added by 50g nano kaoline in 500ml deionized water, under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained Dispersion of Kaolin liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip Dispersion of Kaolin liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/kaolin compounded mix down 100kW is ultrasonic.
The preparation method of Graphene/red light fluorescent powder matrix material is as follows: added by 1g Graphene in 100ml deionized water, and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; By 25 ~ 100gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip red light fluorescent powder dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic.
The preparation method of Graphene/long-afterglow fluorescent powder composite material is as follows: added by 1g Graphene in 100ml deionized water, and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; Added by 25 ~ 100g long persistence luminescent powder in 500ml deionized water, under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained long persistence luminescent powder dispersion liquid after 240 ~ 300 minutes; Down in graphene dispersing solution, slowly drip long persistence luminescent powder dispersion liquid 100kW is ultrasonic, ultrasonic 30 ~ 60min, then suction filtration, oven dry, carry out 1050 DEG C of thermal treatment 30min under vacuum environment, thermal treatment 60min at 1250 DEG C again, obtained Graphene/long-afterglow fluorescent powder composite material.Described long persistence luminescent powder is steady persistence Sr
4al
14o
25nano-phosphor.
(6) graphene/carbon acid calcium/SiO is prepared
2compounded mix, Graphene/kaolin/SiO
2compounded mix, Graphene/red light fluorescent powder/SiO
2matrix material, Graphene/long persistence luminescent powder/SiO
2matrix material:
Graphene/carbon acid calcium/SiO
2compounded mix preparation method is as follows: be scattered in ethanol by graphene/carbon acid calcium compounded mix ultrasonic agitation (400KW ultrasonic vibration and 1000r/min centrifugal speed stir); Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and graphene/carbon acid calcium compounded mix after stirring is 1.8:1, adjust ph is 9, temperature of reaction is 25 DEG C, react 5 hours, carry out centrifugal and obtain precipitation 3 times by acetone and deionized water, washed with de-ionized water successively; This is deposited in 90
odry 2h under C, to obtain being coated with SiO
2graphene/carbon acid calcium/SiO
2compounded mix.
Graphene/kaolin/SiO
2compounded mix preparation method is as follows: be scattered in ethanol by Graphene/kaolin compounded mix ultrasonic agitation (400KW ultrasonic vibration and 1000r/min centrifugal speed stir); Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/kaolin compounded mix after stirring is 1.8:1, adjust ph is 9, temperature of reaction is 25 DEG C, react 5 hours, carry out centrifugal and obtain precipitation 3 times by acetone and deionized water, washed with de-ionized water successively; This is deposited in 90
odry 2h under C, to obtain being coated with SiO
2graphene/kaolin/SiO
2compounded mix.
Graphene/red light fluorescent powder/SiO
2the preparation method of matrix material is as follows: added by 1g Graphene in 100ml deionized water, and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; By 25 ~ 100gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip red light fluorescent powder dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic; 0.5g Graphene/red light fluorescent powder compound material ultrasound being stirred (300 ~ 500KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir) is scattered in ethanol; Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/red light fluorescent powder matrix material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; This is coated with SiO
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; This mixture is immersed in ultrasonic 5 ~ 60min in hydrofluoric acid, removes the silicon-dioxide of part, centrifugal and dry, obtain Graphene/Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06fluorescent material/SiO
2matrix material.
Graphene/long persistence luminescent powder/SiO
2the preparation method of matrix material is as follows: 1g Graphene adds in 100ml deionized water by (a), and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; B 25 ~ 100g long persistence luminescent powder adds in 500ml deionized water by (), under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained long persistence luminescent powder dispersion liquid after 240 ~ 300 minutes; C () slowly drips long persistence luminescent powder dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/long-afterglow fluorescent powder composite material down 100kW is ultrasonic in graphene dispersing solution; D 0.5g Graphene/long persistence luminescent powder compound material ultrasound stirs by () (300 ~ 500KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir) is scattered in ethanol; Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/long-afterglow fluorescent powder composite material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; E this is deposited in 90 by ()
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; F this is coated with SiO by ()
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; G this mixture is immersed in ultrasonic 5 ~ 60min in hydrofluoric acid by (), remove the silicon-dioxide of part, centrifugal and dry, obtains Graphene/long persistence luminescent powder/SiO
2matrix material.
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1
A preparation method for polyamide compoiste material, comprises the following steps:
(1) by 12 parts of Graphene/kaolin/SiO
2compounded mix and 8 parts of graphene/carbon acid calcium/SiO
2compounded mix is scattered in 15 parts of deionized waters under 500KW ultrasonic vibration and 1200r/min centrifugal speed stir, and process 90min forms solution A; Under 800KW ultrasonic vibration and 1000r/min centrifugal speed stir, add 4 parts of Graphenes, process 240min forms mixing suspension;
(2) 50 parts of short glass fibers are added in described suspension, under 300KW ultrasonic vibration and 800r/min centrifugal speed stir, process 90min, leave standstill 60min, remove supernatant liquid, with washed with de-ionized water several, 100 DEG C of dry 90min, obtain mixing glass fiber reinforcements;
(3) material is taken by following portions by weight: nylon resin 70 parts, mix glass fiber reinforcements 40 parts, nylon master batch 5 parts and 0.2 part, oxidation inhibitor; Above-mentioned material is extruded and granulation through twin screw extruder, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 150r/min, and temperature is 265 ~ 280 DEG C, namely obtain polyamide compoiste material, its Mechanics Performance Testing is in table 1.
Embodiment 2
Based on the preparation method of embodiment 1, by 8 parts of graphene/carbon acid calcium/SiO in step (1)
2compounded mix is revised as 0.8 part of graphene/carbon acid calcium/SiO
2compounded mix, all the other are constant, obtain polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Embodiment 3
Based on the preparation method of embodiment 1, by 12 parts of Graphene/kaolin/SiO in step (1)
2compounded mix is revised as 1.2 parts of Graphene/kaolin/SiO
2compounded mix, all the other are constant, obtain polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Comparative example 1.
Based on the preparation method of embodiment 1, by 8 parts of graphene/carbon acid calcium/SiO in step (1)
2compounded mix removes, and all the other are constant, obtains polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Comparative example 2
Based on the preparation method of embodiment 1, removed by 12 parts of Graphene/kaolin/SiO2 compounded mixs in step (1), all the other are constant, obtain polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Comparative example 3
Based on the preparation method of embodiment 1, removed by 4 parts of Graphenes in step (1), all the other are constant, obtain polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Comparative example 4
Based on the preparation method of embodiment 1, by 8 parts of graphene/carbon acid calcium/SiO in step (1)
2compounded mix and 4 parts of Graphenes remove, and all the other are constant, obtain polyamide compoiste material, and its Mechanics Performance Testing is in table 1.
Table 1 the performance test results
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile strength (Mpa) | 195 | 180 | 176 | 150 | 153 | 142 | 134 |
| Flexural strength (Mpa) | 297 | 285 | 280 | 267 | 270 | 254 | 241 |
| Modulus in flexure (Mpa) | 10980 | 9815 | 9634 | 8136 | 8249 | 7898 | 6786 |
Embodiment 4
A preparation method for luminous polyamide matrix material, comprises the following steps:
(1) prepare Graphene/red light fluorescent powder matrix material: added by 1g Graphene in 100ml deionized water, under 800kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 minutes; By 25gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 minutes; In graphene dispersing solution, slowly drip red light fluorescent powder dispersion liquid, ultrasonic 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic;
(2) material is taken by following portions by weight: preparedly in nylon resin 70 parts, embodiment 1 mix glass fiber reinforcements 40 parts, Graphene/1 part, red light fluorescent powder matrix material, nylon master batch 5 parts and 0.2 part, oxidation inhibitor; Extruded and granulation through twin screw extruder by above-mentioned material, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 150r/min, and temperature is 265 ~ 280 DEG C, namely obtains luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material good dispersity, uniformity of luminance is good, and luminous intensity is good.
Embodiment 5
Based on the preparation method of embodiment 4, by the Y in step (1)
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor addition is revised as 50g, and all the other are constant, obtained luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material is better dispersed, and uniformity of luminance is better, and luminous intensity is better.
Embodiment 6
Based on the preparation method of embodiment 4, by the Y in step (1)
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor addition is revised as 100g, and all the other are constant, obtains luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material is dispersed general, and uniformity of luminance is general, and luminous intensity is good.
Comparative example 5
Based on the preparation method of embodiment 4, remove step (1), Graphene/red light fluorescent powder matrix material is revised as red light fluorescent powder, and all the other are constant, obtain luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material dispersiveness is poor, and uniformity of luminance is poor, and luminous intensity is general.
Comparative example 6
Based on the preparation method of embodiment 4, step (1) is revised as:
A () is by 2.4mmolNAVO
412H
2o is dissolved in the mixing solutions containing 10ml ethylene glycol and 3ml distilled water; B above-mentioned solution 300r/min centrifugal speed is stirred below the dropwise Y (NO of instillation containing the certain proportioning of 2.7mmol by ()
3)
36H
2o, Eu (NO
3)
3, Al (NO
3)
3(0.9:0.04:0.06) in 12ml ethylene glycol solution, then clarify to solution at 500r/min centrifugal speed stirring 5 ~ 10min, add the distilled water of 15ml containing 0.01g Graphene; C reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml by (), under vacuum conditions, and 170
oinsulation reaction 90min under C, after reaction terminates, is quickly cooled to room temperature; Gained suspension is poured out, centrifugal and obtain precipitation by acetone and washed with de-ionized water 3 times successively; D this is deposited in 90 by ()
odry 4h under C, obtains graphene/nanometer fluorescent material matrix material; E graphene/nanometer fluorescent material compound material ultrasound stirs by () (500KW ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol; Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and graphene/nanometer fluorescent material matrix material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 6 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; F this is coated with SiO by ()
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain mixture; G this mixture is immersed in ultrasonic 1h in hydrofluoric acid by (), remove silicon-dioxide, centrifugal and dry, obtains Graphene/Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06fluorescent material matrix material.
All the other are constant, obtain luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material bad dispersibility, uniformity of luminance is poor, and luminous intensity is general.
Embodiment 7
A preparation method for luminous polyamide matrix material, comprises the following steps:
(1) Graphene/red light fluorescent powder/SiO is prepared
2matrix material: 1g Graphene adds in 100ml deionized water by (a), under 800kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 minutes; B () is by 25gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 minutes; C () slowly drips red light fluorescent powder dispersion liquid, ultrasonic 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic in graphene dispersing solution; D 0.5g Graphene/red light fluorescent powder compound material ultrasound stirs by () (300KW ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol; Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/red light fluorescent powder matrix material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; E this is deposited in 90 by ()
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; F this is coated with SiO by ()
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; G this mixture is immersed in ultrasonic 5min in hydrofluoric acid by (), remove the silicon-dioxide of part, centrifugal and dry, obtains Graphene/Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06fluorescent material/SiO
2matrix material.
(2) material is taken by following portions by weight: preparedly in nylon resin 70 parts, embodiment 1 mix glass fiber reinforcements 40 parts, Graphene/red light fluorescent powder/SiO
21 part, matrix material, nylon master batch 5 parts and 0.2 part, oxidation inhibitor; Extruded and granulation through twin screw extruder by above-mentioned material, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 150r/min, and temperature is 265 ~ 280 DEG C, namely obtains luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material is better dispersed, and uniformity of luminance is better, and luminous intensity is better.
Embodiment 8
Based on the preparation method of embodiment 7, mixture in step (1) is immersed in ultrasonic time in hydrofluoric acid and is revised as 30min, all the other are constant, obtain luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material dispersiveness is excellent, and uniformity of luminance is excellent, and luminous intensity is excellent.
Embodiment 9
Based on the preparation method of embodiment 7, mixture in step (1) is immersed in ultrasonic time in hydrofluoric acid and is revised as 60min, all the other are constant, obtain luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material is better dispersed, and uniformity of luminance is better, and luminous intensity is good.
Comparative example 7
Based on the preparation method of embodiment 9, remove in step (1) and this is coated with SiO
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h; All the other are constant, obtain luminous polyamide matrix material.
Obtained luminous polyamide matrix material, fluorescent material is dispersed general, and uniformity of luminance is general, and luminous intensity is general.
Embodiment 10
A preparation method for luminous polyamide matrix material, comprises the following steps:
(1) prepare Graphene/long-afterglow fluorescent powder composite material: added by 1g Graphene in 100ml deionized water, under 1000kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 minutes; Added by 25g long persistence luminescent powder in 500ml deionized water, under 1000kW ultrasonic vibration and 800r/min centrifugal speed stir, dispersion obtained long persistence luminescent powder dispersion liquid after 300 minutes; Down in graphene dispersing solution, slowly drip long persistence luminescent powder dispersion liquid 100kW is ultrasonic, ultrasonic 60min, then suction filtration, oven dry, carry out 1050 DEG C of thermal treatment 30min under vacuum environment, thermal treatment 60min at 1250 DEG C again, obtained Graphene/long-afterglow fluorescent powder composite material.
(2) material is taken by following portions by weight: preparedly in nylon resin 70 parts, embodiment 1 mix glass fiber reinforcements 40 parts, Graphene/red light fluorescent powder/SiO
21 part, matrix material, Graphene/long-afterglow fluorescent powder composite material 1 part, nylon master batch 5 parts and 0.2 part, oxidation inhibitor; Extruded and granulation through twin screw extruder by above-mentioned material, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 150r/min, and temperature is 265 ~ 280 DEG C, namely obtains luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 5h, and intensity is good, and uniformity of luminance is good.
Embodiment 11
Based on the preparation method of embodiment 10, the long persistence luminescent powder addition in step (1) is revised as 50g, and all the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 10h, and intensity is better, and uniformity of luminance is better.
Embodiment 12
Based on the preparation method of embodiment 10, the long persistence luminescent powder addition in step (1) is revised as 100g, and all the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 10h, and intensity is good, and uniformity of luminance is general.
Comparative example 8
Based on the preparation method of embodiment 12, remove step (2), in step (3) Graphene/long-afterglow fluorescent powder composite material is replaced to long persistence luminescent powder, all the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material are dispersed general, and intensity is good; The noctilucence sunset glow time is short, and intensity is general, non-uniform light.
Embodiment 13
Based on the preparation method of embodiment 10, Graphene/long-afterglow fluorescent powder composite material prepared by step (1) and be revised as and prepare Graphene/long persistence luminescent powder/SiO
2matrix material, concrete preparation process: 1g Graphene adds in 100ml deionized water by (a), under 1000kW ultrasonic vibration and 500r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 200 minutes; B 25g long persistence luminescent powder adds in 500ml deionized water by (), under 1000kW ultrasonic vibration and 1000r/min centrifugal speed stir, dispersion obtained long persistence luminescent powder dispersion liquid after 240 minutes; C () slowly drips long persistence luminescent powder dispersion liquid down 100kW is ultrasonic in graphene dispersing solution, ultrasonic 60min, then suction filtration, oven dry, carry out 1050 DEG C of thermal treatment 30min under vacuum environment, thermal treatment 60min at 1250 DEG C again, obtained Graphene/long-afterglow fluorescent powder composite material; D 0.5g Graphene/long persistence luminescent powder compound material ultrasound stirs by () (500KW ultrasonic vibration and 1000r/min centrifugal speed stir) is scattered in ethanol; Add a certain proportion of (5:1) water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/long-afterglow fluorescent powder composite material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; E this is deposited in 90 by ()
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; F this is coated with SiO by ()
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; G this mixture is immersed in ultrasonic 5min in hydrofluoric acid by (), remove the silicon-dioxide of part, centrifugal and dry, obtains Graphene/long persistence luminescent powder/SiO
2matrix material;
All the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 11h, and intensity is better, and uniformity of luminance is better.
Embodiment 14
Based on the preparation method of embodiment 13, mixture in step (1) is immersed in ultrasonic time in hydrofluoric acid and is revised as 30min, all the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 12h, and intensity is excellent, and uniformity of luminance is more excellent.
Embodiment 15
Based on the preparation method of embodiment 13, mixture in step (1) is immersed in ultrasonic time in hydrofluoric acid and is revised as 60min, all the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 10.5h, and intensity is general, and uniformity of luminance is good.
Comparative example 9
Based on the preparation method of embodiment 15, remove in step (1) and this is coated with SiO
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h; All the other are constant, obtain luminous polyamide matrix material.
Obtain luminous polyamide matrix material, two kinds of fluorescent material good dispersitys, and intensity is good; Noctilucence sunset glow is for up to 10h, and intensity difference, uniformity of luminance is poor.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (9)
1. a preparation method for luminous polyamide matrix material, comprises the following steps:
(1) prepare Graphene/red light fluorescent powder matrix material: added by 1g Graphene in 100ml deionized water, under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; By 25 ~ 100gY
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor adds in 500ml deionized water, and under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained red light fluorescent powder dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip red light fluorescent powder dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/red light fluorescent powder matrix material down 100kW is ultrasonic;
(2) Graphene/red light fluorescent powder/SiO is prepared
2matrix material: 0.5g Graphene/red light fluorescent powder matrix material is scattered in ethanol under 300 ~ 500KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir; Add a certain proportion of water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/red light fluorescent powder matrix material after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 12 hours; Carry out centrifugal and obtain precipitation 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell composite material; This is coated with SiO
2core-shell composite material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1.5h, obtain mixture; This mixture is immersed in ultrasonic 5 ~ 60min in hydrofluoric acid, removes the silicon-dioxide of part, centrifugal and dry, obtain Graphene/Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06fluorescent material/SiO
2matrix material;
(3) material is taken by following portions by weight: nylon resin 60 ~ 70 parts, mix glass fiber reinforcements 30 ~ 40 parts, nylon master batch 1 ~ 5 part, Graphene/red light fluorescent powder/SiO
21 ~ 5 part, matrix material and 0.1 ~ 0.3 part, oxidation inhibitor; Extruded and granulation through twin screw extruder by above-mentioned material, the wherein said glass fiber reinforcements that mixes is added by side feeding, and the screw speed of described twin screw extruder is 120 ~ 150r/min, and temperature is 265 ~ 280 DEG C, namely obtains polyamide compoiste material.
2. the preparation method of luminous polyamide matrix material according to claim 1, is characterized in that, described Graphene is obtained by following methods: get a certain amount of sour flat band ink, 1000 DEG C process 1 hour, then at 7%H in atmosphere
2nitrogen and hydrogen mixture in 1000 DEG C of in-situ reducing process 1.5 hours, add the macrogol ester of mass ratio 3% and tetracarboxylic dianhydride's dinaphthyl of mass ratio 5.0% again, the slurry that concentration is 80.0% is made into water, first under power is the ultrasonic assistant of 400W, carry out 3500 revs/min of ball millings 8 hours, 2000 revs/min of ball millings are carried out 4 hours under being adjusted to 200W ultrasonic wave again, through supercentrifuge 10000 revs/min separation after ball milling, lyophilize, obtains Graphene solid.
3. the preparation method of luminous polyamide matrix material according to claim 1, is characterized in that, described Y
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano fluorescent powder, preparation method thereof is as follows: (a) is by 2.4mmolNa
3vO
412H
2o is dissolved in the mixing solutions containing 10ml ethylene glycol and 3ml distilled water; B above-mentioned solution 300r/min centrifugal speed is stirred below the dropwise Y (NO of instillation containing the certain proportioning of 2.7mmol by ()
3)
36H
2o, Eu (NO
3)
3, Al (NO
3)
312ml ethylene glycol solution in, then 500r/min centrifugal speed stir 5 ~ 10min clarify to solution, add 15ml distilled water; C reaction soln is poured in the polytetrafluoroethyllining lining autoclave that volume is 50ml by (), under vacuum conditions, and 170
oinsulation reaction 90min under C, after reaction terminates, is quickly cooled to room temperature; Gained suspension is poured out, centrifugal and obtain white precipitates by acetone and washed with de-ionized water 3 times successively; D this is deposited in 90 by ()
ounder C, dry 4h, obtains nano-phosphor; E nano-phosphor ultrasonic agitation is scattered in ethanol by (); Add a certain proportion of water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and nano-phosphor after stirring is 1.8:1, and adjust ph is 9, and temperature of reaction is 25 DEG C, reacts 6 hours; Carry out centrifugal and obtain white precipitate 3 times by acetone and washed with de-ionized water successively; This is deposited in 90
odry 5h under C, to obtain being coated with SiO
2core-shell nano fluorescent material; F this is coated with SiO by ()
2core-shell nano fluorescent material be placed in argon gas atmosphere under carry out 800 DEG C of thermal treatment 1h, obtain fluorescent material mixture; G fluorescent material mixture is immersed in ultrasonic 1h in hydrofluoric acid by (), remove silicon-dioxide, centrifugal and dry, obtains the Y of median size 10 ~ 20nm
0.9vO
4: Eu
3+ 0.04, Al
3+ 0.06nano-phosphor.
4. the preparation method of fluorescent polyamide matrix material according to claim 1, is characterized in that, described in mix the preparation method of glass fiber reinforcements as follows:
(1) be scattered in 15 ~ 20 parts of deionized waters by 10 ~ 15 parts of Graphene/kaolin/SiO2 compounded mixs and 5 ~ 10 parts of graphene/carbon acid calcium/SiO2 compounded mixs under 500 ~ 800KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir, process 90 ~ 120min forms solution A; Under 500 ~ 800KW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir, add 1 ~ 5 part of Graphene, process 240 ~ 300min forms mixing suspension;
(2) 40 ~ 50 parts of short glass fibers are added in described suspension, process 90 ~ 120min under 300 ~ 500KW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, leave standstill 60min, remove supernatant liquid, with washed with de-ionized water several, 100 DEG C of dry 90min, obtain mixing glass fiber reinforcements.
5. the preparation method of luminous polyamide matrix material according to claim 4, is characterized in that, graphene/carbon acid calcium/SiO
2compounded mix preparation method is as follows: be scattered in ethanol by graphene/carbon acid calcium compounded mix ultrasonic agitation; Add a certain proportion of water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and graphene/carbon acid calcium compounded mix after stirring is 1.8:1, adjust ph is 9, temperature of reaction is 25 DEG C, react 5 hours, carry out centrifugal and obtain precipitation 3 times by acetone and deionized water, washed with de-ionized water successively; This is deposited in 90
odry 2h under C, to obtain being coated with SiO
2graphene/carbon acid calcium/SiO
2compounded mix.
6. the preparation method of luminous polyamide matrix material according to claim 5, it is characterized in that, the preparation method of described graphene/carbon acid calcium compounded mix is as follows: added by 1g Graphene in 100ml deionized water, under 800 ~ 1000kW ultrasonic vibration and 500 ~ 1000r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; Add in 500ml deionized water by 100g quantum dot calcium carbonate, under 1200 ~ 1500kW ultrasonic vibration and 1000 ~ 1200r/min centrifugal speed stir, dispersion obtained calcium carbonate dispersion liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip calcium carbonate dispersion liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained graphene/carbon acid calcium compounded mix down 100kW is ultrasonic.
7. the preparation method of luminous polyamide matrix material according to claim 4, is characterized in that, Graphene/kaolin/SiO
2compounded mix preparation method is as follows: by Graphene/kaolin compounded mix ultrasonic agitation is scattered in ethanol; Add a certain proportion of water and ammoniacal liquor afterwards, the mass ratio adding tetraethoxy and Graphene/kaolin compounded mix after stirring is 1.8:1, adjust ph is 9, temperature of reaction is 25 DEG C, react 5 hours, carry out centrifugal and obtain precipitation 3 times by acetone and deionized water, washed with de-ionized water successively; This is deposited in 90
odry 2h under C, to obtain being coated with SiO
2graphene/kaolin/SiO
2compounded mix.
8. the preparation method of luminous polyamide matrix material according to claim 7, it is characterized in that, the preparation method of described Graphene/kaolin compounded mix is as follows: added by 1g Graphene in 100ml deionized water, and under 800 ~ 1000kW ultrasonic vibration and 500 ~ 800r/min centrifugal speed stir, dispersion obtained graphene dispersing solution after 180 ~ 200 minutes; Added by 50g nano kaoline in 500ml deionized water, under 1000 ~ 1200kW ultrasonic vibration and 800 ~ 1000r/min centrifugal speed stir, dispersion obtained Dispersion of Kaolin liquid after 240 ~ 300 minutes; In graphene dispersing solution, slowly drip Dispersion of Kaolin liquid, ultrasonic 30 ~ 60min, then suction filtration, oven dry, obtained Graphene/kaolin compounded mix down 100kW is ultrasonic.
9. the preparation method of luminous polyamide matrix material according to claim 8, it is characterized in that, the preparation method of described nano-kaoline is as follows: by 150g kaolin ore with the rotating speed ball milling 60 minutes of 1500 revs/min, then insert in 5L deionized water, add 220g Potassium ethanoate and stir 60 minutes, suction filtration cleaning is about 7 to pH value, then with the rotating speed ball milling 60 minutes of 1200 revs/min after drying under 80 degree of conditions, carry out 1800 revs/min of ball millings under being adjusted to 300W ultrasonic wave again 1 hour, obtain the kaolin powder of particle diameter at 10 ~ 30nm.
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Application publication date: 20160323 |