CN106221153A - A kind of modified ABS/PLA luminescent composite - Google Patents
A kind of modified ABS/PLA luminescent composite Download PDFInfo
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- CN106221153A CN106221153A CN201610605768.0A CN201610605768A CN106221153A CN 106221153 A CN106221153 A CN 106221153A CN 201610605768 A CN201610605768 A CN 201610605768A CN 106221153 A CN106221153 A CN 106221153A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
- C09K11/655—Aluminates; Silicates
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of modified ABS/PLA luminescent composite, it is made up of the raw material of following weight portion meter: polylactic acid 40 ~ 50 parts, substance law ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile glycidyl methacrylate copolymer 5 ~ 10 parts, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, conductive filler 5 ~ 10 parts, fluorescent material complex 3 ~ 8 parts, graphene quantum dot and porous graphene；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Composite；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, and it is 0.1 ~ 2% that described porous graphene accounts for the percentage by weight of ABS gross weight.Described ABS/PLA luminescent composite, not only has the mechanics electric property of excellence, and has optimal luminescent properties, widened the range of application of 3D printed material further；Solving in prior art, add fluorescent material, particularly nanoscale fluorescent material, reunites the most in the composite, and reduces its characteristics of luminescence.
Description
Technical field
The present invention relates to field of compound material, a kind of ABS/PLA luminescent composite printed for 3D.
Background technology
3D printing technique is also known as a kind of emerging technology of increasing material manufacturing technology, actually rapid shaping field, and it is one
Kind based on mathematical model file, use powdery metal or plastics etc. can jointing material, come by the way of successively printing
The technology of constructed object.Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid.At present, 3D beats
Print technology is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes these tradition and depends on
The retrofit technique relied.It addition, 3D printing technique is gradually applied to the necks such as medical science, biological engineering, building, clothing, aviation
Territory, has opened up wide space for innovation.
At present, the high connductivity needed for ABS/PLA conducing composite material is applicable to double end 3D printing technique in prior art
Material strip material, but it has Characteristics of Long Luminosity to yet there are no relevant report, therefore, need badly research and development one have high connductivity and
There is the ABS/PLA composite of excellent luminance characteristic.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of modified ABS/PLA luminescent composite, no
Only there is the mechanics electric property of excellence, and there is optimal luminescent properties, widened the application of 3D printed material further
Scope；Solving in prior art, add fluorescent material, particularly nanoscale fluorescent material, reunites the most in the composite,
And reduce its characteristics of luminescence.
The technical problem to be solved is achieved by the following technical programs:
A kind of modified ABS/PLA luminescent composite, it is made up of the raw material of following weight portion meter: polylactic acid 40 ~ 50 parts, body
Method ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 ~ 10
Part, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, conductive filler 5 ~ 10 parts, fluorescent material complex 3 ~ 8 parts, graphene quantum dot
And porous graphene；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Compound
Thing；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, and described porous graphene accounts for the weight of ABS gross weight
Amount percentage ratio is 0.1 ~ 2%.
Described ABS/PLA luminescent composite preparation method is as follows:
(1) pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300
Mesh powder, is scattered in pure water, and ultrasonic (power 200 ~ 300W) after 1 hour, ultrasonic limit, limit microwave exposure (2500 ~ 3000MHz,
Temperature controls at 80 ~ 90 DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
(2) PLA/ material with carbon element master batch is prepared: weigh CNT and be placed in beaker, addition chloroform, limit high-speed stirred (1000 ~
1400r/min), limit ultrasonic (power 300 ~ 500KW) 3 hours, obtain carbon nano tube suspension, standby；In heating-up temperature (50 ~ 60
DEG C) under, half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution, be divided into two first part, second
Part PLA solution, standby；Under temperature constant state (50 ~ 60 DEG C), the ultrasonic (power in limit high-speed stirred (1000 ~ 1400r/min) limit
300 ~ 500KW) first part of PLA solution, drip carbon nano tube suspension, ultrasonic agitation 30 ~ 60min；Continue dropping second part
PLA solution, ultrasonic agitation 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain carbon
Material polylactic acid mixed liquor；What material with carbon element polylactic acid mixed liquor was passed through spray dryer stocks in groove, with 200～300ml/
Material with carbon element polylactic acid mixed liquor is ejected in spray dryer by the speed of min, is dried to obtain PLA/ material with carbon element master batch；Described spraying
The nozzle diameter of exsiccator is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(3) prepare PLA/ fluorescent material master batch: by fluorescent material complex ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~
1400r/min centrifugal speed stirs) it is scattered in pure water, obtain fluorescent material complex solution, standby；In heating-up temperature (50 ~ 60
DEG C) under, second half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution, be divided into two the 3rd part,
Four parts of PLA solution, standby；Under temperature constant state (50 ~ 60 DEG C), the ultrasonic (power in limit high-speed stirred (1000 ~ 1400r/min) limit
300 ~ 500KW) the 3rd part of PLA solution, drip fluorescent material complex solution, ultrasonic agitation 30 ~ 60min；Continue dropping the 4th
Part PLA solution, ultrasonic agitation 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain
Fluorescent material polylactic acid mixed liquor；What fluorescent material polylactic acid mixed liquor was passed through spray dryer stocks in groove, with 200～300ml/
Fluorescent material polylactic acid mixed liquor is ejected in spray dryer by the speed of min, is dried to obtain PLA/ fluorescent material master batch；Described spraying
The nozzle diameter of exsiccator is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(4) Graphene modified ABS master batch is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, land in container
Continuous addition substance law ABS (Tao Shi MAGNUM 213), emulsion method ABS (Taiwan very U.S. 747) and porous graphene, high-speed stirred 30
~ 60min is sufficiently mixed；The mixture obtained feeding rotating nozzle spray dryer is spray-dried, inlet temperature 185
DEG C, quickly cooled down by spray drying exit and obtain Graphene modified ABS master batch；
(5) by PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and Graphene modified ABS master batch, styrene-acrylonitrile-
Glycidyl methacrylate copolymer (SAN-GMA), butyltriphenylphosphonium bromide phosphine (TPB) mix, through double screw extruder
At 185 DEG C, carry out melt blending, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then through material strip shaping mechanism
Make the 3D printing ABS/PLA luminescence material strip of modification.
In the present invention, described fluorescent material is long lad phosphor.
In the present invention, described long lad phosphor is Sr4Al14O25Nano-phosphor or ZnS quantum dot fluorescent material.
In the present invention, described Sr4Al14O25Nano-phosphor mean diameter is the fluorescent material less than 10nm.
In the present invention, described organic solvent is by acetone, butanone, 2 pentanone, propione, Ketocyclopentane, isopropyl methyl first
At least one in ketone, oxolane and dioxane is constituted.
In the present invention, described Graphene/SiO2/ fluorescent material is prepared by following methods: Graphene ultrasonic agitation disperseed
In ethanol；Adding 3:1 water and ammonia afterwards, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:
1, regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively
Obtain precipitation；This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2
Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；By the core-shell composite material submergence after heat treatment
Ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2
Powder adds in 100ml deionized water, makes after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir
Obtain Graphene/SiO2Dispersion liquid；1 ~ 100 part of fluorescent material is added in 500ml deionized water, at 1200kW ultrasonic vibration and
Fluorescent material dispersion liquid is prepared after the lower dispersion 300min of 1000r/min centrifugal speed stirring；100kW ultrasonic lower toward Graphene/
SiO2Dispersion liquid is slowly added dropwise fluorescent material dispersion liquid, ultrasonic 50min, then sucking filtration, drying, under vacuum environment, carries out 1050
DEG C heat treatment 60min, prepares Graphene/SiO2/ fluorescent material.
In the present invention, described Graphene/SiO2/ fluorescent material/SiO2Composite is prepared by following methods: by Graphene
Ultrasonic agitation is scattered in ethanol；Add 3:1 water and ammonia afterwards, be stirring evenly and then adding into the matter of tetraethyl orthosilicate and Graphene
Amount ratio is 1.8:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 12 hours；Be centrifuged and successively with acetone and go from
Sub-water cleans 3 times and obtains precipitation；This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；Should
It is coated with SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Nucleocapsid after heat treatment is multiple
Condensation material is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried stone
Ink alkene/SiO2Powder adds in 100ml deionized water, disperses under 800kW ultrasonic vibration and 800r/min centrifugal speed stir
Graphene/SiO is prepared after 120min2Dispersion liquid；1 ~ 100 part of fluorescent material is added in 500ml deionized water, ultrasonic at 1200kW
Fluorescent material dispersion liquid is prepared after vibrations and the lower dispersion 300min of 1000r/min centrifugal speed stirring；Ultrasonic lower toward graphite at 100kW
Alkene/SiO2Dispersion liquid is slowly added dropwise fluorescent material dispersion liquid, ultrasonic 50min, then sucking filtration, drying, carries out under vacuum environment
1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/ fluorescent material；By Graphene/SiO2/ fluorescent material ultrasonic agitation is scattered in second
In alcohol；Add 3:1 water and ammonia afterwards, be stirring evenly and then adding into tetraethyl orthosilicate and Graphene/SiO2The mass ratio of/fluorescent material
For 1.5:1, regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 5 hours；It is centrifuged and successively with acetone and deionized water
Clean 3 times and obtain precipitation；This is deposited in 90oIt is dried 5h under C, obtains Graphene/SiO2/ fluorescent material/SiO2Complex.
There is advantages that
Obtaining scientific matching by test of many times, prepared described ABS/PLA luminescent composite not only has the mechanics of excellence
Electric property, and there is optimal luminescent properties, widen the range of application of 3D printed material further；Solve existing
In technology, adding fluorescent material, particularly nanoscale fluorescent material, reunites the most in the composite, reduces its characteristics of luminescence.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ material with carbon element master batch: weigh 9.7 parts of CNTs and be placed in beaker, adds chloroform, limit high-speed stirred
(1200r/min), limit ultrasonic (power 400KW) 3 hours, obtain carbon nano tube suspension, standby；Under heating-up temperature (60 DEG C),
Being dissolved in organic solvent by 20 parts of pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain first part, second part of poly-breast
Acid solution, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of poly-breast
Acid solution, drips carbon nano tube suspension, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation
60min, obtains material with carbon element polylactic acid mixed liquor；What material with carbon element polylactic acid mixed liquor was passed through spray dryer stocks in groove, with
Material with carbon element polylactic acid mixed liquor is ejected in spray dryer by the speed of 300ml/min, is dried to obtain PLA/ material with carbon element master batch；Institute
The nozzle diameter stating spray dryer is 0.6mm, and dry air flow rates is at 30m3/ h, temperature 150 DEG C；
3, preparation PLA/ fluorescent material master batch: by 4.5 parts of fluorescent material complex ultrasonic agitation (500KW ultrasonic vibration and 1300r/min
Centrifugal speed stirs) it is scattered in pure water, obtain fluorescent material complex solution, standby；Under heating-up temperature (60 DEG C), pre-by 20 parts
Processing polylactic acid to be dissolved in organic solvent, obtain PLA solution, be divided into two to obtain the 3rd part, the 4th part of PLA solution,
Standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution,
Dropping fluorescent material complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min, obtain
To fluorescent material polylactic acid mixed liquor；What fluorescent material polylactic acid mixed liquor was passed through spray dryer stocks in groove, with 300ml/min
Speed fluorescent material polylactic acid mixed liquor is ejected in spray dryer, be dried to obtain PLA/ fluorescent material master batch；Described spray dried
The nozzle diameter of dry device is 0.6mm, and dry air flow rates is at 30m3/ h, temperature 150 DEG C；
4, PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213), breast
Liquid method ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts, SAN-
GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mixing, at 185 DEG C, carry out melt blending through double screw extruder, system
For going out there is the co-continuous ABS/PLA alloy of fluorescent characteristic, then send out through the 3D printing ABS/PLA that material strip forming machine manufacture is modified
Light material strip.
Wherein, described fluorescent material complex is Graphene/SiO2/ fluorescent material, it is prepared by following methods: surpassed by Graphene
Sound stirring (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；Add a certain proportion of afterwards
(3:1) water and ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:1, and regulation pH value is 9, instead
Answering temperature is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is sunk
Form sediment 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2Core-shell composite material put
800 DEG C of heat treatment 1.5h are carried out under argon gas atmosphere；Core-shell composite material after heat treatment is immersed in Fluohydric acid. ultrasonic
1min, removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder add 100ml go from
In sub-water, after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir, prepare Graphene/SiO2Dispersion
Liquid；50 parts of nanoscale long lad phosphors are added in 500ml deionized waters, 1200kW ultrasonic vibration and 1000r/min from
Long lad phosphor dispersion liquid is prepared after the lower dispersion 300min of heart speed stirring；Ultrasonic lower toward Graphene/SiO at 100kW2Dispersion
Liquid is slowly added dropwise long lad phosphor dispersion liquid, ultrasonic 50min, then sucking filtration, drying, under vacuum environment, carries out 1050 DEG C
Heat treatment 60min, prepares Graphene/SiO2/ long-afterglow fluorescent flour complexes.Described long lad phosphor is long afterglow
Sr4Al14O25Nano-phosphor, mean diameter is the fluorescent material less than 10nm.
Embodiment 2
Preparation method based on embodiment 1, the difference is that only:
Graphene/SiO2/ fluorescent material is prepared by following methods: by Graphene ultrasonic agitation (700KW ultrasonic vibration and 1300r/
Min centrifugal speed stirs) it is scattered in ethanol；Add a certain proportion of (3:1) water and ammonia afterwards, be just stirring evenly and then adding into
Silester is 1.8:1 with the mass ratio of Graphene, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 12 hours；Carry out from
The heart also cleans 3 acquisition precipitations with acetone and deionized water successively；This is deposited in 90o5h it is dried, to be coated with under C
SiO2Core-shell composite material；This is coated with SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatments
1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, centrifugal
And be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, at 800kW ultrasonic vibration and 800r/
Graphene/SiO is prepared after the lower dispersion 120min of min centrifugal speed stirring2Dispersion liquid；50 parts of nanoscale long lad phosphors are added
Enter in 500ml deionized water, prepare long after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir
Persistence phosphor dispersion liquid；Ultrasonic lower toward Graphene/SiO at 100kW2Dispersion liquid is slowly added dropwise long lad phosphor dispersion
Liquid, ultrasonic 50min, then sucking filtration, drying, under vacuum environment, carry out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/
Long-afterglow fluorescent flour complexes.Described long lad phosphor is long afterglow Sr4Al14O25Nano-phosphor, mean diameter is for being less than
The fluorescent material of 10nm.
Embodiment 3
Preparation method based on embodiment 1, the difference is that only:
Graphene/SiO2/ fluorescent material is prepared by following methods: by Graphene ultrasonic agitation (700KW ultrasonic vibration and 1300r/
Min centrifugal speed stirs) it is scattered in ethanol；Add a certain proportion of (3:1) water and ammonia afterwards, be just stirring evenly and then adding into
Silester is 1.8:1 with the mass ratio of Graphene, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 12 hours；Carry out from
The heart also cleans 3 acquisition precipitations with acetone and deionized water successively；This is deposited in 90o5h it is dried, to be coated with under C
SiO2Core-shell composite material；This is coated with SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatments
1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 30min in Fluohydric acid., removes the silicon dioxide of part, centrifugal
And be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, at 800kW ultrasonic vibration and 800r/
Graphene/SiO is prepared after the lower dispersion 120min of min centrifugal speed stirring2Dispersion liquid；50 parts of nanoscale long lad phosphors are added
Enter in 500ml deionized water, prepare long after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir
Persistence phosphor dispersion liquid；Ultrasonic lower toward Graphene/SiO at 100kW2Dispersion liquid is slowly added dropwise long lad phosphor dispersion
Liquid, ultrasonic 50min, then sucking filtration, drying, under vacuum environment, carry out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/
Long-afterglow fluorescent flour complexes.Described long lad phosphor is long afterglow Sr4Al14O25Nano-phosphor, mean diameter is for being less than
The fluorescent material of 10nm.
Embodiment 4
Preparation method based on embodiment 1, the difference is that only: Graphene/SiO2/ fluorescent material is prepared by following methods: will
Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；Add certain afterwards
(3:1) water of ratio and ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:1, regulates pH value
Being 9, reaction temperature is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；
This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2Nucleocapsid be combined
Material is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in Fluohydric acid.
Ultrasonic 15min, removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder adds 100ml
In deionized water, after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir, prepare Graphene/SiO2
Dispersion liquid；10 parts of nanoscale long lad phosphors are added in 500ml deionized water, at 1200kW ultrasonic vibration and 1000r/
Long lad phosphor dispersion liquid is prepared after the lower dispersion 300min of min centrifugal speed stirring；100kW ultrasonic lower toward Graphene/
SiO2Dispersion liquid is slowly added dropwise long lad phosphor dispersion liquid, ultrasonic 50min, then sucking filtration, drying, enters under vacuum environment
1050 DEG C of heat treatment 60min of row, prepare Graphene/SiO2/ long-afterglow fluorescent flour complexes.Described long lad phosphor is for long remaining
Brightness Sr4Al14O25Nano-phosphor, mean diameter is the fluorescent material less than 10nm.
Embodiment 5
Preparation method based on embodiment 1, the difference is that only: Graphene/SiO2/ fluorescent material is prepared by following methods: will
Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；Add certain afterwards
(3:1) water of ratio and ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:1, regulates pH value
Being 9, reaction temperature is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；
This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2Nucleocapsid be combined
Material is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in Fluohydric acid.
Ultrasonic 15min, removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder adds 100ml
In deionized water, after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir, prepare Graphene/SiO2
Dispersion liquid；100 parts of nanoscale long lad phosphors are added in 500ml deionized water, at 1200kW ultrasonic vibration and 1000r/
Long lad phosphor dispersion liquid is prepared after the lower dispersion 300min of min centrifugal speed stirring；100kW ultrasonic lower toward Graphene/
SiO2Dispersion liquid is slowly added dropwise long lad phosphor dispersion liquid, ultrasonic 50min, then sucking filtration, drying, enters under vacuum environment
1050 DEG C of heat treatment 60min of row, prepare Graphene/SiO2/ long-afterglow fluorescent flour complexes.Described long lad phosphor is for long remaining
Brightness Sr4Al14O25Nano-phosphor, mean diameter is the fluorescent material less than 10nm.
Embodiment 6
Preparation method based on embodiment 1, the difference is that only: Graphene/SiO2/ fluorescent material changes into Graphene/SiO2/
Fluorescent material/SiO2Complex, it prepares by following methods:
(1) Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) is scattered in ethanol；It
A certain proportion of (3:1) water of rear addition and ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:
1, regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively
Obtain precipitation；This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material；This is coated with SiO2
Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；By the core-shell composite material submergence after heat treatment
Ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder
End adds in 100ml deionized water, prepares after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir
Graphene/SiO2Dispersion liquid；10 parts of nanoscale long lad phosphors are added in 500ml deionized water, in the ultrasonic shake of 1200kW
Long lad phosphor dispersion liquid is prepared after the lower dispersion 300min of dynamic and 1000r/min centrifugal speed stirring；Ultrasonic lower past at 100kW
Graphene/SiO2Being slowly added dropwise long lad phosphor dispersion liquid in dispersion liquid, ultrasonic 50min, then sucking filtration, drying, in vacuum
Carry out 1050 DEG C of heat treatment 60min under environment, prepare Graphene/SiO2/ long-afterglow fluorescent flour complexes.
(2) by Graphene/SiO2/ long-afterglow fluorescent flour complexes ultrasonic agitation (500KW ultrasonic vibration and 800r/min from
Heart speed stirs) it is scattered in ethanol；Add a certain proportion of (3:1) water and ammonia afterwards, be stirring evenly and then adding into positive silicic acid
Ethyl ester and Graphene/SiO2The mass ratio of/long-afterglow fluorescent flour complexes is 1.5:1, and regulation pH value is 9, and reaction temperature is 25
DEG C, react 5 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 5h, obtains Graphene/SiO2/ fluorescent material/SiO2Complex.
Described long lad phosphor is long afterglow Sr4Al14O25Nano-phosphor, mean diameter is the fluorescence less than 10nm
Powder.
Embodiment 7
Preparation method based on embodiment 2, difference is: CNT is changed into Graphene, using quantum dot ZnS as
Long lad phosphor.
Embodiment 8
Based on embodiment 1, difference is:
1, pretreatment polylactic acid raw material: polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) is ground into 300 mesh
Powder, is scattered in pure water, and ultrasonic (power 250W), after 1 hour, (2800MHz, temperature controls 85 ultrasonic limit, limit microwave exposure
DEG C) 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
2, preparation PLA/ material with carbon element master batch: weigh 9.7 parts of CNTs and be placed in beaker, adds chloroform, limit high-speed stirred
(1200r/min), limit ultrasonic (power 400KW) 3 hours, obtain carbon nano tube suspension, standby；Under heating-up temperature (60 DEG C),
Being dissolved in organic solvent by 20 parts of pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain first part, second part of poly-breast
Acid solution, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of poly-breast
Acid solution, drips carbon nano tube suspension, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation
60min；(described graphene quantum dot accounts for the mass percent of described half polylactic acid to continue dropping graphene quantum dot solution
0.5%), ultrasonic agitation 60min, obtain material with carbon element polylactic acid mixed liquor；Material with carbon element polylactic acid mixed liquor is passed through spray dryer
Stock in groove, with the speed of 300ml/min, material with carbon element polylactic acid mixed liquor is ejected in spray dryer, be dried to obtain PLA/
Material with carbon element master batch；The nozzle diameter of described spray dryer is 0.6mm, and dry air flow rates is at 30m3/ h, temperature 150 DEG C；
3, preparation PLA/ fluorescent material master batch: by 4.5 parts of fluorescent material complex ultrasonic agitation (500KW ultrasonic vibration and 1300r/min
Centrifugal speed stirs) it is scattered in pure water, obtain fluorescent material complex solution, standby；Under heating-up temperature (60 DEG C), pre-by 20 parts
Processing polylactic acid to be dissolved in organic solvent, obtain PLA solution, be divided into two to obtain the 3rd part, the 4th part of PLA solution,
Standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 500KW) the 3rd part of PLA solution,
Dropping fluorescent material complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min；Continue
Continuous dropping graphene quantum dot solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described half polylactic acid), super
Sound stirring 60min, obtains fluorescent material polylactic acid mixed liquor；What fluorescent material polylactic acid mixed liquor was passed through spray dryer stocks groove
In, with the speed of 300ml/min, fluorescent material polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ fluorescent material mother
Grain；The nozzle diameter of described spray dryer is 0.6mm, and dry air flow rates is at 30m3/ h, temperature 150 DEG C；
4, at room temperature with under the speed conditions of 1500r/min, add successively in container substance law ABS (21.78 parts, Tao Shi
MAGNUM 213), (porous graphene accounts for the matter of ABS gross mass for emulsion method ABS (17 parts, Taiwan very U.S. 747) and porous graphene
Amount percent is 1%), high-speed stirred 60min is sufficiently mixed；The mixture obtained feeding rotating nozzle spray dryer is entered
Row is spray-dried, and inlet temperature 185 DEG C is quickly cooled down by spray drying exit and obtains Graphene modified ABS master batch；
5, by PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and Graphene modified ABS master batch, styrene-acrylonitrile-first
Base glycidyl acrylate copolymer (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through double spiral shells
Bar extruder carries out melt blending at 185 DEG C, prepares the co-continuous ABS/PLA alloy with fluorescent characteristic, then through material strip
Forming machine manufactures modified 3D and prints by ABS/PLA luminescence material strip.
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；Described stone
The preparation method of ink alkene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphite
Alkene quantum dot, is scattered in second further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed)
In alcohol, this is only a kind of embodiment, it is also possible to obtain by other means.
Embodiment 9
Based on embodiment 8, difference is: it is 0.8% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous
It is 0.5% that Graphene accounts for the mass percent of ABS gross mass.
Embodiment 10
Based on embodiment 8, difference is: it is 1% that described graphene quantum dot accounts for the mass percent of polylactic acid；Porous stone
It is 2% that ink alkene accounts for the mass percent of ABS gross mass.
Comparative example 1
Preparation method based on embodiment 1, difference is: described fluorescent material complex is Sr4Al14O25Nano-phosphor,
Mean diameter is the fluorescent material less than 10nm.
Comparative example 2
Preparation method based on embodiment 1, difference is: described fluorescent material complex is fluorescent material/SiO2Composite,
It is prepared by following methods:
Long lad phosphor ultrasonic agitation (500KW ultrasonic vibration and the stirring of 800r/min centrifugal speed) is scattered in ethanol；
Add a certain proportion of (3:1) water and ammonia afterwards, be stirring evenly and then adding into the quality of tetraethyl orthosilicate and long lad phosphor
Ratio is 1.5:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 6 hours；It is centrifuged and successively with acetone and deionization
Water cleans 3 times and obtains precipitation；This is deposited in 90o5h it is dried, to obtain being coated with SiO under C2Core-shell composite material, in vacuum
Carry out 1050 DEG C of heat treatment 60min under environment, obtain fluorescent material/SiO2Complex.
Comparative example 3
Based on embodiment 1, difference is: luminescent composite preparation method is as follows:
1, weighing CNT to be placed in beaker, add chloroform, limit high-speed stirred, limit, after ultrasonic 8 hours, adds half PLA, continues
Ultrasonic and stirring 4 hours, after mixture is air-dried, is placed in 120 DEG C of baking ovens 4 hours, obtains PLA/ material with carbon element master batch；
2, second half PLA and fluorescent material complex add in banbury melt blending at 185 DEG C, and preparation PLA/ fluorescent material is female
Grain；
3, by PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213),
Emulsion method ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts,
SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mixing, through double screw extruder carry out at 185 DEG C melted altogether
Mixed, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then the 3D printing ABS/ through material strip forming machine manufacture modification
PLA luminescence material strip.
Comparative example 4
Based on embodiment 1, difference is: luminescent composite preparation method is as follows:
1, weighing CNT to be placed in beaker, add chloroform, limit high-speed stirred, limit, after ultrasonic 8 hours, adds half PLA, continues
Ultrasonic and stirring 4 hours, after mixture is air-dried, is placed in 120 DEG C of baking ovens 4 hours, obtains PLA/ material with carbon element master batch；
2, second half PLA and fluorescent material complex add in banbury melt blending at 185 DEG C, and preparation PLA/ fluorescent material is female
Grain；
3, by PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and substance law ABS (21.78 parts, Tao Shi MAGNUM 213),
Emulsion method ABS (17 parts, Taiwan very U.S. 747), styrene-acrylonitrile-glycidyl methacrylate copolymer (5 parts,
SAN-GMA), Graphene 0.8 part, butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mix, through double screw extruder in 185 DEG C
Under carry out melt blending, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture through material strip forming machine modified
3D prints by ABS/PLA luminescence material strip.
Table 1 is embodiment 1 ~ 10 and comparative example 1 ~ 4 records machinery and electric conductivity data and luminescent properties data
Table 1
| Real Execute Example 1 | Real Execute Example 2 | Real Execute Example 3 | Real Execute Example 4 | Real Execute Example 5 | Real Execute Example 6 | Real Execute Example 8 | Implement Example 9 | Implement Example 10 | Contrast Example 1 | Contrast Example 2 | Contrast Example 3 | Contrast Example 4 | |
| Stretch-proof Intensity Mpa | 48. 23 | 49. 25 | 48. 36 | 48. 58 | 47. 78 | 48. 28 | 92. 45 | 93.5 6 | 93.3 2 | 46.8 5 | 45.88 | 40.15 | 43.66 |
| Breach rushes Hit intensity J/M | 136 | 137 | 131 | 132 | 129 | 138 | 280 | 292 | 285 | 105 | 102 | 98 | 110 |
| Volume electricity Resistance rate Ω·cm | 0.5 3 | 0.5 2 | 0.5 5 | 0.5 7 | 0.5 6 | 0.5 2 | 0.3 3 | 0.31 | 0.35 | 0.75 | 0.71 | 0.76 | 0.58 |
| Luminous equal Even property | Good | Relatively Good | Good | Good | One As | Excellent | Good | Good | Good | Very poor | Poor | Difference | Difference |
| Long afterglow Time | Long Reach 8h | Long Reach 10h | Long Reach 8h | Long Reach 8h | Long Reach 8h | Long Reach 12h | Long Reach 8h | It is up to 8h | It is up to 8h | It is up to 4h | It is up to 4h | It is up to 4h | It is up to 4h |
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained
Case, all should fall within the scope and spirit of the invention.
Claims (6)
1. modified ABS/PLA luminescent composite, it is made up of the raw material of following weight portion meter: polylactic acid 40 ~ 50 part,
Body method ABS20 ~ 25 part, emulsion method ABS10 ~ 20 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 ~
10 parts, butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05 part, conductive filler 5 ~ 10 parts, fluorescent material complex 3 ~ 8 parts, Graphene quantum
Point and porous graphene；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Multiple
Compound；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polylactic acid, and described porous graphene accounts for ABS gross weight
Percentage by weight is 0.1 ~ 2%；
Described ABS/PLA luminescent composite preparation method is as follows:
(1) pretreatment polylactic acid raw material: polylactic acid raw material is ground into 300 mesh powder, is scattered in pure water, after ultrasonic 1 hour,
Ultrasonic limit, limit microwave exposure 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polylactic acid；
(2) PLA/ material with carbon element master batch is prepared: weigh CNT and be placed in beaker, add chloroform, limit high-speed stirred, limit ultrasonic 3
Hour, obtain carbon nano tube suspension, standby；At the heating temperature, half pretreatment polylactic acid is dissolved in organic solvent,
To PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Under temperature constant state, high-speed stirred limit, limit surpasses
First part of PLA solution of sound, drips carbon nano tube suspension, ultrasonic agitation 30 ~ 60min；Continue second part of polylactic acid of dropping molten
Liquid, ultrasonic agitation 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain the poly-breast of material with carbon element
Acid mixed liquor；What material with carbon element polylactic acid mixed liquor was passed through spray dryer stocks in groove, with the speed of 200～300ml/min
Material with carbon element polylactic acid mixed liquor is ejected in spray dryer, is dried to obtain PLA/ material with carbon element master batch；
(3) PLA/ fluorescent material master batch is prepared: fluorescent material complex ultrasonic agitation be scattered in pure water, obtain fluorescent material complex molten
Liquid, standby；At the heating temperature, second half pretreatment polylactic acid is dissolved in organic solvent, obtains PLA solution, one point
Be two the 3rd part, the 4th part of PLA solution, standby；Under temperature constant state, the ultrasonic 3rd part of polylactic acid in high-speed stirred limit, limit is molten
Liquid, drips fluorescent material complex solution, ultrasonic agitation 30 ~ 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 30 ~
60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain fluorescent material polylactic acid mixed liquor；By fluorescence
What powder polylactic acid mixed liquor was passed through spray dryer stocks in groove, and fluorescent material polylactic acid is mixed by the speed with 200～300ml/min
Close liquid to be ejected in spray dryer, be dried to obtain PLA/ fluorescent material master batch；
(4) Graphene modified ABS master batch is prepared: at room temperature with under the speed conditions of 1000 ~ 1500r/min, land in container
Continuous addition substance law ABS, emulsion method ABS and porous graphene, high-speed stirred 30 ~ 60min is sufficiently mixed；The mixture that will obtain
Send into rotating nozzle spray dryer to be spray-dried, inlet temperature 185 DEG C, quickly cooled down by spray drying exit
To Graphene modified ABS master batch；
(5) by PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch and Graphene modified ABS master batch, styrene-acrylonitrile-
Glycidyl methacrylate copolymer, butyltriphenylphosphonium bromide phosphine mix, and melt at 185 DEG C through double screw extruder
Melt blended, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing use through material strip forming machine
ABS/PLA luminescence material strip.
Modified ABS the most according to claim 1/PLA luminescent composite, it is characterised in that described fluorescent material is for long remaining
Brightness fluorescent material.
Modified ABS the most according to claim 2/PLA luminescent composite, it is characterised in that described long lad phosphor
For Sr4Al14O25Nano-phosphor or ZnS quantum dot fluorescent material.
Modified ABS the most according to claim 3/PLA luminescent composite, it is characterised in that described Sr4Al14O25Nanometer
Fluorescent material mean diameter is the fluorescent material less than 10nm.
Modified ABS the most according to claim 1/PLA luminescent composite, it is characterised in that described Graphene/SiO2/ glimmering
Light powder is prepared by following methods: Graphene ultrasonic agitation be scattered in ethanol；Add 3:1 water and ammonia afterwards, stir
Rear addition tetraethyl orthosilicate is 1.8:1 with the mass ratio of Graphene, and regulation pH value is 9, and reaction temperature is 25 DEG C, and reaction 12 is little
Time；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90o5h it is dried under C, with
To being coated with SiO2Core-shell composite material；This is coated with SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C
Heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the titanium dioxide of part
Silicon, is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, at 800kW ultrasonic vibration
Graphene/SiO is prepared after dispersion 120min lower with the stirring of 800r/min centrifugal speed2Dispersion liquid；1 ~ 100 part of fluorescent material is added
In 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare fluorescence
Powder dispersion liquid；Ultrasonic lower toward Graphene/SiO at 100kW2Dispersion liquid is slowly added dropwise fluorescent material dispersion liquid, ultrasonic 50min, so
Rear sucking filtration, drying, carry out 1050 DEG C of heat treatment 60min under vacuum environment, prepares Graphene/SiO2/ fluorescent material.
Modified ABS the most according to claim 1/PLA luminescent composite, it is characterised in that described Graphene/SiO2/ glimmering
Light powder/SiO2Composite is prepared by following methods: Graphene ultrasonic agitation be scattered in ethanol；Afterwards add 3:1 water and
Ammonia, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and Graphene is 1.8:1, and regulation pH value is 9, and reaction temperature is
25 DEG C, react 12 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90oC
Under be dried 5h, to obtain being coated with SiO2Core-shell composite material；This is coated with SiO2Core-shell composite material be placed in argon gas
800 DEG C of heat treatment 1.5h are carried out under atmosphere；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., goes
Except the silicon dioxide of part, it is centrifuged and is dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water,
Graphene/SiO is prepared after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；By 1 ~
100 parts of fluorescent material add in 500ml deionized water, disperse under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir
Fluorescent material dispersion liquid is prepared after 300min；Ultrasonic lower toward Graphene/SiO at 100kW2Dispersion liquid is slowly added dropwise fluorescent material dispersion
Liquid, ultrasonic 50min, then sucking filtration, drying, under vacuum environment, carry out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/
Fluorescent material；By Graphene/SiO2/ fluorescent material ultrasonic agitation is scattered in ethanol；Add 3:1 water and ammonia afterwards, stir
Rear addition tetraethyl orthosilicate and Graphene/SiO2The mass ratio of/fluorescent material is 1.5:1, and regulation pH value is 9, and reaction temperature is 25
DEG C, react 5 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 5h, obtains Graphene/SiO2/ fluorescent material/SiO2Complex.
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| CN109265946A (en) * | 2018-09-28 | 2019-01-25 | 吕梁学院 | A kind of quantum dot light emitting compound and preparation method thereof for 3D printing |
| CN111057538A (en) * | 2019-12-30 | 2020-04-24 | 广州工程技术职业学院 | Luminescent material containing rare earth europium complex and preparation method thereof |
| US11034709B2 (en) * | 2019-05-29 | 2021-06-15 | The Hong Kong University Of Science And Technology | Organic long persistence luminescence compositions |
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| CN105419309A (en) * | 2015-12-18 | 2016-03-23 | 黄志华 | Preparation method of luminescent polyamide composite material |
| CN105694190A (en) * | 2016-01-27 | 2016-06-22 | 苏州翠南电子科技有限公司 | Magnetic plastic material |
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| CN103804942A (en) * | 2014-02-12 | 2014-05-21 | 厦门凯纳石墨烯技术有限公司 | Graphene-containing insulated radiating composition and preparation and application thereof |
| CN105001586A (en) * | 2015-07-14 | 2015-10-28 | 暨南大学 | Electric conduction compound ABS/PLA material for 3D printing wires as well as preparation method and application of electric conduction compound ABS/PLA material |
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| US11034709B2 (en) * | 2019-05-29 | 2021-06-15 | The Hong Kong University Of Science And Technology | Organic long persistence luminescence compositions |
| CN111057538A (en) * | 2019-12-30 | 2020-04-24 | 广州工程技术职业学院 | Luminescent material containing rare earth europium complex and preparation method thereof |
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