CN106009573A - ABS/PLA (acrylonitrile-butadiene-styrene/poly lactic acid) light-emitting composite material for 3D (three-dimensional) printing - Google Patents

ABS/PLA (acrylonitrile-butadiene-styrene/poly lactic acid) light-emitting composite material for 3D (three-dimensional) printing Download PDF

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CN106009573A
CN106009573A CN201610605460.6A CN201610605460A CN106009573A CN 106009573 A CN106009573 A CN 106009573A CN 201610605460 A CN201610605460 A CN 201610605460A CN 106009573 A CN106009573 A CN 106009573A
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pla
fluorescent material
sio
graphene
ultrasonic
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黎淑娟
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Foshan Gaoming Technology Co Ltd
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Foshan Gaoming Technology Co Ltd
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses an ABS/PLA (acrylonitrile-butadiene-styrene/poly lactic acid) light-emitting composite material for 3D (three-dimensional) printing. The ABS/PLA light-emitting composite material is prepared from the following raw materials in parts by weight: 40 to 50 parts of polylactic acid, 20 to 25 parts of bulk type ABS, 10 to 20 parts of emulsion type ABS, 5 to 10 parts of styrene-acrylonitrile-methacrylic acidglycidyl ester copolymer, 0.01 to 0.05 part of butyl-triphenyl phosphonium bromide, 5 to 10 parts of conductive filler, and 3 to 8 parts of fluorescent powder compound, wherein the fluorescent powder compound is a graphene/SiO2 (silicon dioxide)/fluorescent powder or graphene/SiO2/fluorescent powder/SiO2 composite material. The ABS/PLA light-emitting composite material has the advantages that the mechanical and electrical properties are excellent, the light emitting property is optimum, and the application range of the 3D printing material is widened; the problem of decreasing of light-emitting property due to easy agglomeration of fluorescent powder (especially nano-fluorescent powder) in the composite material in the prior art is solved.

Description

A kind of 3D Print ABS/PLA Luminescent composite
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 increasing a kind of emerging technology of material manufacturing technology, actually rapid shaping field, and it is a kind of based on mathematical model file, use powdery metal or plastics etc. can jointing material, by the way of successively printing, carry out the technology of constructed object.Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid.At present, 3D printing technique is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes the retrofit technique that these tradition rely on.It addition, 3D printing technique is gradually applied to the fields such as medical science, biological engineering, building, clothing, aviation, open up wide space for innovation.
At present, high connductivity material strip material needed for ABS/PLA conducing composite material is applicable to double end 3D printing technique in prior art, but it has Characteristics of Long Luminosity to yet there are no relevant report, therefore, a kind of ABS/PLA composite that there is high connductivity and there is excellent luminance characteristic of research and development is needed badly.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides the ABS/PLA luminescent composite that a kind of 3D prints, not only there is the mechanics electric property of excellence, and there is 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.
The technical problem to be solved is achieved by the following technical programs:
The ABS/PLA luminescent composite that a kind of 3D prints, 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；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Complex；
Described ABS/PLA luminescent composite preparation method is as follows:
(1) pretreatment polylactic acid raw material: by polylactic acid raw material (D, PLLA raw material, weight average molecular weight 100,000) it is ground into 300 mesh powder, it is scattered in pure water, ultrasonic (power 200 ~ 300W) is 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, add chloroform, limit high-speed stirred (1000 ~ 1400r/min), limit ultrasonic (power 300 ~ 500KW) 3 hours, obtain carbon nano tube suspension, standby；Under heating-up temperature (50 ~ 60 DEG C), being dissolved in organic solvent by half pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Under temperature constant state (50 ~ 60 DEG C), limit high-speed stirred (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW) first part of PLA solution, drip carbon nano tube suspension, ultrasonic agitation 30 ~ 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 30 ~ 60min, obtain 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, and material with carbon element polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried and to obtain PLA/ material with carbon element master batch；The nozzle diameter of described spray dryer is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(3) PLA/ fluorescent material master batch is prepared: fluorescent material complex ultrasonic agitation (300 ~ 500KW ultrasonic vibration and the stirring of 1000 ~ 1400r/min centrifugal speed) be scattered in pure water, obtain fluorescent material complex solution, standby；Under heating-up temperature (50 ~ 60 DEG C), being dissolved in organic solvent by second half pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；Under temperature constant state (50 ~ 60 DEG C), limit high-speed stirred (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW) the 3rd part of PLA solution, drip fluorescent material complex solution, ultrasonic agitation 30 ~ 60min；Continue the 4th part of PLA solution of dropping, 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, and fluorescent material polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried and to obtain PLA/ fluorescent material master batch；The nozzle diameter of described spray dryer is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature 120～160 DEG C；
(4) PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch mix with substance law ABS, emulsion method ABS, styrene-acrylonitrile-glycidyl methacrylate copolymer, butyltriphenylphosphonium bromide phosphine, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
In the present invention, described ABS/PLA luminescent composite is made up of the raw material of following weight portion meter: polylactic acid 42 parts, substance law ABS21.78 part, emulsion method ABS17 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 parts, butyltriphenylphosphonium bromide phosphine 0.02 part, conductive filler 9.7 parts, fluorescent material complex 4.5 parts.
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 made up of at least one in acetone, butanone, 2 pentanone, propione, Ketocyclopentane, methyl isopropyl ketone, oxolane and dioxane.
In the present invention, described Graphene/SiO2/ fluorescent material is prepared by following methods: Graphene ultrasonic agitation be scattered 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, and 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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion 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 fluorescent material dispersion liquid；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, carries out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/ fluorescent material.
In the present invention, described Graphene/SiO2/ fluorescent material/SiO2Composite is prepared by following methods: Graphene ultrasonic agitation be scattered 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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion 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 fluorescent material dispersion liquid；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, carries 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, be stirring evenly and then adding into 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, reacts 5 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining 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 electric property of excellence, and has optimal luminescent properties, has 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, 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, it is scattered in pure water, ultrasonic (power 250W) after 1 hour, ultrasonic limit, limit microwave exposure (2800MHz, temperature controls at 85 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, obtains 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 PLA solution, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, drip carbon nano tube suspension, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min, obtain 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, is ejected in spray dryer by material with carbon element polylactic acid mixed liquor with the speed of 300ml/min, is dried and 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: 4.5 parts of fluorescent material complex ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) are scattered in pure water, obtain fluorescent material complex solution, 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 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, drip fluorescent material complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min, obtain fluorescent material polylactic acid mixed liquor；What fluorescent material polylactic acid mixed liquor was passed through spray dryer stocks in groove, is ejected in spray dryer by fluorescent material polylactic acid mixed liquor with the speed of 300ml/min, is dried and to obtain PLA/ fluorescent material 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；
4, 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, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
Wherein, described fluorescent material complex is Graphene/SiO2/ fluorescent material, it is prepared by following methods: Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) be scattered in ethanol；Adding a certain proportion of (3:1) water and ammonia afterwards, 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, 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；50 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries 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 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: Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) be scattered in ethanol；Adding a certain proportion of (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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；50 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries 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 the fluorescent material less than 10nm.
Embodiment 3
Preparation method based on embodiment 1, the difference is that only:
Graphene/SiO2/ fluorescent material is prepared by following methods: Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) be scattered in ethanol；Adding a certain proportion of (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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 30min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；50 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries 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 the fluorescent material less than 10nm.
Embodiment 4
Preparation method based on embodiment 1, the difference is that only: Graphene/SiO2/ fluorescent material is prepared by following methods: Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) be scattered in ethanol；Adding a certain proportion of (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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；10 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries 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 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: Graphene ultrasonic agitation (700KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) be scattered in ethanol；Adding a certain proportion of (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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；100 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries 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 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；Adding a certain proportion of (3:1) water and ammonia afterwards, 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, 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 15min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion liquid；10 parts of nanoscale long lad phosphors are added in 500ml deionized water, after disperseing 300min under 1200kW ultrasonic vibration and 1000r/min centrifugal speed stir, prepare long lad 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, carries out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/ long-afterglow fluorescent flour complexes.
(2) by Graphene/SiO2/ long-afterglow fluorescent flour complexes 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 tetraethyl orthosilicate 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, reacts 5 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90oIt is dried 5h under C, obtains Graphene/SiO2/ fluorescent material/SiO2Complex.
Described long lad phosphor is long afterglow Sr4Al14O25Nano-phosphor, mean diameter is the fluorescent material less than 10nm.
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, it is scattered in pure water, ultrasonic (power 250W) after 1 hour, ultrasonic limit, limit microwave exposure (2800MHz, temperature controls at 85 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, obtains 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 PLA solution, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) limit ultrasonic (power 400KW) first part of PLA solution, drip carbon nano tube suspension, ultrasonic agitation 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 60min；Continue dropping graphene quantum dot solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), ultrasonic agitation 60min, obtain 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, is ejected in spray dryer by material with carbon element polylactic acid mixed liquor with the speed of 300ml/min, is dried and 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: 4.5 parts of fluorescent material complex ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1300r/min centrifugal speed) are scattered in pure water, obtain fluorescent material complex solution, 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 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, drip fluorescent material complex solution, ultrasonic agitation 60min；Continue the 4th part of PLA solution of dropping, ultrasonic agitation 60min；Continue dropping graphene quantum dot solution (it is 0.5% that described graphene quantum dot accounts for the mass percent of described polylactic acid), ultrasonic agitation 60min, obtain fluorescent material polylactic acid mixed liquor；What fluorescent material polylactic acid mixed liquor was passed through spray dryer stocks in groove, is ejected in spray dryer by fluorescent material polylactic acid mixed liquor with the speed of 300ml/min, is dried and to obtain PLA/ fluorescent material 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；
4, at room temperature with under the speed conditions of 1500r/min, substance law ABS (21.78 parts is added successively in container, Tao Shi MAGNUM 213), emulsion method ABS (17 parts, Taiwan very U.S. 747) and porous graphene (it is 1% that porous graphene accounts for the mass percent of ABS gross mass), high-speed stirred 60min is sufficiently mixed；The mixture obtained feeding rotating nozzle spray dryer is spray-dried, inlet temperature 185 DEG C, is 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 (5 parts, SAN-GMA), butyltriphenylphosphonium bromide phosphine (0.02 part, TPB) mixing, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；The preparation method of described graphene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphene quantum dot, being scattered in ethanol further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed), 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；It is 0.5% that porous 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；It is 2% that porous graphene 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 prepares by following methods:
Long lad phosphor ultrasonic agitation (500KW ultrasonic vibration and the stirring of 800r/min centrifugal speed) is scattered in ethanol；Adding a certain proportion of (3:1) water and ammonia afterwards, the mass ratio being stirring evenly and then adding into tetraethyl orthosilicate and long lad phosphor is 1.5:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, reacts 6 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, under vacuum environment, carry out 1050 DEG C of heat treatment 60min, 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 are added in banbury melt blending at 185 DEG C, prepares PLA/ fluorescent material master batch；
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, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
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 are added in banbury melt blending at 185 DEG C, prepares PLA/ fluorescent material master batch；
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) mixing, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
Table 1 is embodiment 1 ~ 10 and comparative example 1 ~ 4 records machinery and electric conductivity data and luminescent properties data
Table 1
Embodiment described above only have expressed embodiments of the present invention; it describes more 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 using the form of equivalent or equivalent transformation to be obtained, all should fall within the scope and spirit of the invention.

Claims (7)

1. the ABS/PLA luminescent composite that 3D prints, 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；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Complex；
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, ultrasonic 3 hours of limit, obtain carbon nano tube suspension, standby；At the heating temperature, being dissolved in organic solvent by half pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain first part, second part of PLA solution, standby；Under temperature constant state, the ultrasonic first part of PLA solution in high-speed stirred limit, limit, drip carbon nano tube suspension, ultrasonic agitation 30 ~ 60min；Continue second part of PLA solution of dropping, ultrasonic agitation 30 ~ 60min, obtain 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, and material with carbon element polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried and to obtain PLA/ material with carbon element master batch；
(3) prepare PLA/ fluorescent material master batch: fluorescent material complex ultrasonic agitation be scattered in pure water, obtain fluorescent material complex solution, standby；At the heating temperature, being dissolved in organic solvent by second half pretreatment polylactic acid, obtain PLA solution, be divided into two to obtain the 3rd part, the 4th part of PLA solution, standby；Under temperature constant state, the ultrasonic 3rd part of PLA solution in high-speed stirred limit, limit, drip fluorescent material complex solution, ultrasonic agitation 30 ~ 60min；Continue the 4th part of PLA solution of dropping, 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, and fluorescent material polylactic acid mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried and to obtain PLA/ fluorescent material master batch；
(4) PLA/ material with carbon element conductive agglomerate, PLA/ fluorescent material master batch mix with substance law ABS, emulsion method ABS, styrene-acrylonitrile-glycidyl methacrylate copolymer, butyltriphenylphosphonium bromide phosphine, at 185 DEG C, melt blending is carried out through double screw extruder, prepare the co-continuous ABS/PLA alloy with fluorescent characteristic, then manufacture modified 3D printing ABS/PLA luminescence material strip through material strip forming machine.
The ABS/PLA luminescent composite that 3D the most according to claim 1 prints, it is characterized in that, described ABS/PLA luminescent composite is made up of the raw material of following weight portion meter: polylactic acid 42 parts, substance law ABS21.78 part, emulsion method ABS17 part, styrene-acrylonitrile-glycidyl methacrylate copolymer 5 parts, butyltriphenylphosphonium bromide phosphine 0.02 part, conductive filler 9.7 parts, fluorescent material complex 4.5 parts；Described fluorescent material complex is Graphene/SiO2/ fluorescent material or Graphene/SiO2/ fluorescent material/SiO2Complex.
The ABS/PLA luminescent composite that 3D the most according to claim 1 and 2 prints, it is characterised in that described fluorescent material is long lad phosphor.
The ABS/PLA luminescent composite that 3D the most according to claim 3 prints, it is characterised in that described long lad phosphor is Sr4Al14O25Nano-phosphor or ZnS quantum dot fluorescent material.
The ABS/PLA luminescent composite that 3D the most according to claim 4 prints, it is characterised in that described Sr4Al14O25Nano-phosphor mean diameter is the fluorescent material less than 10nm.
The ABS/PLA luminescent composite that 3D the most according to claim 1 and 2 prints, it is characterised in that described Graphene/SiO2/ fluorescent material is prepared by following methods: Graphene ultrasonic agitation be scattered 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, and 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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion 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 fluorescent material dispersion liquid；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, carries out 1050 DEG C of heat treatment 60min, prepare Graphene/SiO2/ fluorescent material.
The ABS/PLA luminescent composite that 3D the most according to claim 1 and 2 prints, it is characterised in that described Graphene/SiO2/ fluorescent material/SiO2Composite is prepared by following methods: Graphene ultrasonic agitation be scattered 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, and 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 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 SiO2Core-shell composite material be placed under argon gas atmosphere and carry out 800 DEG C of heat treatment 1.5h；Core-shell composite material after heat treatment is immersed in ultrasonic 1 ~ 30min in Fluohydric acid., removes the silicon dioxide of part, be centrifuged and be dried；Take 1 part of dried Graphene/SiO2Powder adds in 100ml deionized water, prepares Graphene/SiO after disperseing 120min under 800kW ultrasonic vibration and 800r/min centrifugal speed stir2Dispersion 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 fluorescent material dispersion liquid；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, carries 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, be stirring evenly and then adding into 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, reacts 5 hours；It is centrifuged and cleans 3 times with acetone and deionized water successively obtaining precipitation；This is deposited in 90oIt is dried 5h under C, obtains Graphene/SiO2/ fluorescent material/SiO2Complex.
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