CN113789030B - Sustainable-luminescence 3D printing ABS composite material and preparation method thereof - Google Patents

Sustainable-luminescence 3D printing ABS composite material and preparation method thereof Download PDF

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CN113789030B
CN113789030B CN202111199483.9A CN202111199483A CN113789030B CN 113789030 B CN113789030 B CN 113789030B CN 202111199483 A CN202111199483 A CN 202111199483A CN 113789030 B CN113789030 B CN 113789030B
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abs
powder
printing
fluorescent powder
sustainable
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CN113789030A (en
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曾巍
张苗
雷玉彤
管洁
闵魁英
蒋佩良
王亮
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Lanzhou Fire Rescue Detachment
Northwest Normal University
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Lanzhou Fire Rescue Detachment
Northwest Normal University
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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a sustainable luminous 3D printing ABS composite material and a preparation method thereof, wherein long afterglow fluorescent powder, KH550, ABS particles and ABS powder are respectively taken; adding KH550 into deionized water, hydrolyzing and stirring, adding fluorescent powder, refluxing, cooling, washing, vacuum drying to constant weight, and grinding to obtain KH550 modified fluorescent powder; after the ABS powder is acidified by hydrochloric acid, the ABS powder is grafted with fluorescent powder modified by KH550 through HATU, so that a composite material is obtained; the composite material is manufactured by melting through a 3D printing extruder, and the 3D printing ABS composite material capable of continuously emitting light is obtained by extrusion and drawing. The preparation method realizes the combination of the long afterglow luminescent material and the 3D printing technology, and the prepared 3D printing composite material not only can continuously emit light, but also has good mechanical properties, can be applied to the aspects of medicine, manufacturing industry, food industry, jewelry industry and the like, and greatly expands the application field of 3D printing.

Description

Sustainable-luminescence 3D printing ABS composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer materials and 3D printing materials, and relates to a sustainable luminescent 3D printing ABS composite material and a preparation method thereof.
Background
In recent years, additive manufacturing, also known as 3D printing, has rapidly progressed, becoming an important processing technique. The method can be used for rapidly printing prototypes with complex geometric shapes and has the advantages of low cost, high adaptability, material saving and the like. The method is a processing technology which is quite opposite to the traditional material removal processing method: firstly, a three-dimensional model is simulated and sliced in a computer, and a three-dimensional structure is decomposed into a plurality of layers of two-dimensional structures; then melting the printing consumables at high temperature, and performing layer-by-layer spray extrusion printing through a spray head; and finally forming the three-dimensional structure device which is identical to the design model. Compared with the removal processing, the 3D printing raw material is less in waste and less in manpower resource consumption, so that the method is favored in the field of material processing.
The 3D printing technique was developed by charles-helter (the parent of 3D printing) in 1984 at the earliest. In 2005, the first high definition color 3D printer on the market was developed successfully by ZCorp. In 2018, russian astronauts printed the thyroid gland of the laboratory mice under zero gravity using a 3D bio-printer of the international space station. 3D printing in China is developed from 1988 to date, and the situation of continuous deepening and continuous expanding of application is presented. Not only can large-sized parts be manufactured by 3D printing equipment, but also small-sized parts can be finished smoothly, and single crystal blades can be printed.
3D printing is regarded as one of core technologies leading a new technological revolution and industrial revolution, and has wide development prospect. With the economic development and the improvement of living standard, the 3D printing is combined with the technologies of robots, artificial intelligence and the like, so that the flexibility degree of a manufacturing production line is improved, customized products are produced at lower cost, and the manufacturing production mode is promoted to be changed from mass production to personalized customization. Meanwhile, 3D printing will push the manufacturing industry to develop to a local manufacturing mode by virtue of saving warehouse and logistics costs and fast response to the local market. In addition, the deep popularization of 3D printing education will promote the rising of the movement of creating guests, and home printers and small-sized 3D printing shops are more popular, and people can manufacture products designed by themselves. In the future, with the development of 3D printers, materials and post-processing technologies, the application field of 3D printing will be expanding.
Common materials for 3D printing are ABS, PLA, PC material, nylon material, and the like. ABS is currently the most productive and widely used polymer, organically unifying the various properties of PS, SAN, BS, and has the characteristics of toughness, hardness, and rigidity. ABS plastic has the characteristics of excellent heat resistance, impact resistance, low temperature resistance, chemical resistance, electrical property, stable product size and the like, and becomes the first choice consumable for 3D printing. At present, ABS is mainly prefabricated into filaments and powdered for use, and the application range almost covers all daily necessities, engineering necessities and part of mechanical necessities, and is widely applied to the fields of automobiles, household appliances and electronic consumer goods.
The 3D printing material has rich color and no luminous characteristic, limits the application of the 3D printing material in the fluorescent fields such as safety marks and the like, and has poor mechanical properties. The long afterglow luminescent material mainly comprises rare earth metal doped metal sulfide and alkaline earth metal aluminate. The rare earth metal doped alkaline earth metal silicate has excellent long-lasting luminescence property, stable chemical property and excellent hydrolysis resistance. The excitation wavelength range of the silicate luminescent material is quite wide, the shortest wavelength is less than 300nm, and the longest wavelength can reach 500nm. Sr (Sr) 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ Can continuously emit light for several hours, and is expected to become a representative of a new generation of silicate long afterglow materials.
Disclosure of Invention
The invention aims to provide a sustainable luminous 3D printing ABS composite material, which can obviously improve the mechanical property and the luminous property.
The invention further aims to provide a preparation method of the 3D printing composite material, and the fluorescent powder and the 3D printing raw material are combined to break through the single limit of the 3D printing material, so that the 3D printing technology can be widely applied to various industries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a sustainable luminescent 3D printed ABS composite material which is a filament with a diameter of 1.75±0.03mm.
The other technical scheme adopted by the invention is as follows: the preparation method of the 3D printing ABS composite material comprises the following steps:
1) According to the mass percentage, 1 to 3 percent of long afterglow fluorescent powder, (3-aminopropyl) triethoxysilane (KH 550) 1 to 3 percent, 88 to 90 percent of ABS particles and 6 to 8 percent of ABS powder are respectively taken, and the total amount of each component is 100 percent; the long afterglow fluorescent powder is Sr 2 MgSi 2 O 7 Europium-dysprosium doped fluorescent powder; dividing the ABS powder into two parts, wherein the mass of the first part of ABS powder is 1-3% of that of the ABS powder, and the mass of the second part of ABS powder is 97-99% of that of the ABS powder;
the long afterglow fluorescent powder is Enhanced afterglow properties of Nd published in J Ceramics International according to 2016 3+ co-doped Sr 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ synthesized by sol-gel method.
2) Adding 1-3 mL (3-aminopropyl) triethoxysilane into 50mL deionized water, adding the obtained (3-aminopropyl) triethoxysilane into the deionized water, hydrolyzing and stirring for 5-10 min, adding the obtained long afterglow fluorescent powder, refluxing at 70-80 ℃ for 10-24 h (the rotating speed is 200-500 r/min), naturally cooling to room temperature, centrifuging, filtering and washing with deionized water for multiple times, removing unreacted KH550, drying to constant weight at 70-80 ℃ in a vacuum drying oven, and grinding to obtain modified fluorescent powder (KH 550 modified fluorescent powder);
3) Adding 1-5 g of ABS powder into 50mL of hydrochloric acid, adding a first part of ABS powder into the hydrochloric acid, refluxing for 10-24 h at the temperature of 100-120 ℃ at the rotating speed of 200-500 r/min, naturally cooling to room temperature, centrifuging, filtering and washing with ethanol and deionized water for multiple times, removing unreacted hydrochloric acid, drying to constant weight at the temperature of 70-80 ℃ in a vacuum drying oven, and grinding to obtain acidified ABS;
4) Taking 1-1.3 eq of 0- (7-azabenzotriazole-1-yl) -N, N, N ', N' -tetramethyl urea Hexafluorophosphate (HATU) according to the proportion of 1-3 g of acidified ABS, completely dissolving the acidified ABS prepared in the step 3) into N, N-Dimethylformamide (DMF), adding HATU, activating for 5-10 min, adding modified fluorescent powder, stirring at room temperature for 3-5 h (the rotating speed is 200-500 r/min), centrifuging, filtering and washing with deionized water for multiple times, drying to constant weight at 70-80 ℃ in a vacuum drying oven, and grinding to obtain ABS grafted fluorescent powder;
5) Uniformly mixing the ABS grafted fluorescent powder, the ABS particles and the second part of ABS powder to obtain a sustainable luminescent 3D printing blend;
6) And (3) loading the sustainable-luminous 3D printing blend into a 3D printing extruder for melt manufacturing, wherein the melt temperature is 235-250 ℃, and extruding, drawing and wiredrawing are carried out to prepare the sustainable-luminous 3D printing composite filament, namely the sustainable-luminous 3D printing ABS composite material.
The following are performance tests:
1) XRD pattern:
FIG. 1 shows that, compared with the long afterglow phosphor, the KH550 modified phosphor and the ABS grafted phosphor have a spectrum peak value corresponding to Sr 2 MgSi 2 O 7 Is matched to the relative intensities of the other elements. Eu due to similar electronegativity and radius 2+ And Dy 3+ Substituted Sr 2 MgSi 2 O 7 Middle Sr 2 + Is a position of (c). No additional peaks of other phases were found, nor significant lattice distortion occurred, indicating that Sr after modification and grafting 2 MgSi 2 O 7 But also retains its own crystal structure.
2) Infrared spectroscopy:
FIG. 2 shows that the long afterglow phosphor is at 2922cm -1 Where there is-CH 2 Is a symmetrical bending vibration peak of (2). KH550 modified fluorescent powder has the absorption peak and is 1582cm -1 There appears a distinct absorption peak of-C.ident.N at 1067cm -1 The Si-O absorption peak appears, which indicates that the long afterglow fluorescent powder and KH550 are condensed and coated on the surface of the fluorescent powder, namely the fluorescent powder is successfully modified.
FIG. 3 shows that 3059cm -1 、3026cm -1 There is a benzene ring=ch stretching vibration peak, 2923cm -1 Presence of-CH 2 -asymmetric stretching vibration peak, 2849cm -1 Where there is-CH 2 -symmetrical telescopic vibration peak 2237cm -1 There is a-C.ident.N stretching vibration peak of 1634cm -1 There was a C=C stretching vibration peak at 1602cm -1 、1492cm -1 、1452cm -1 There is benzene ring-C=C-bending vibration 1381cm -1 At which-CH bending vibration is present, 1068cm -1 、4028cm -1 The position is attributed to mono-substituted benzene ring=ch in-plane deformation, 965cm -1 Ascribed to-ch=ch-out-of-plane deformation. Acidifying with hydrochloric acid, 1759cm -1 The stretching vibration peak at-c=o appears, indicating that hydrochloric acid successfully acidifies-c≡n of ABS.
FIG. 4 shows that at 1510cm -1 An amide bond c=o peak appears at 1260cm -1 C-N peak appears at the place, showing Sr 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ Grafting with ABS was successful.
According to the preparation method, KH550 is adopted to carry out organic modification on the long-afterglow fluorescent powder prepared by a sol-gel method. KH550 is characterized by having a readily hydrolyzable (alcoholysis) group at one end and-NH at the other end 2 . The surface of the fluorescent powder is easy to absorb a layer of water film, silane reacts with the water on the surface of the fluorescent powder, silicon hydroxyl is formed by hydrolysis, then hydrogen bond is formed with the hydroxyl on the surface of the fluorescent powder or condensed into-SiO-M covalent bond (M is Sr or Mg), silanol among molecules of the silane is condensed with each other, and oligomerization forms a netty film to cover the surface of the fluorescent powder, so that the water resistance of the powder and the compatibility of the fluorescent powder and ABS are improved on the basis of not affecting the optical performance of the fluorescent powder, the fluorescent powder and the ABS are uniformly dispersed, and meanwhile, the mechanical strength of the composite material is also improved.
Although ABS has excellent mechanical properties and excellent impact strength, and can be used at extremely low temperature, ABS powder has poor fluidity, pure ABS powder is difficult to extrude by an extruder, and the application of the ABS powder in the field of 3D printing is affected, so that the preparation method disclosed by the invention mixes ABS particles with ABS powder. Tests prove that the mechanical property of the ABS particle and ABS powder mixed extrusion spline is higher than that of the ABS particle extrusion spline.
The ABS particles are hard in texture, difficult to acidify and difficult to graft with fluorescent powder, and the subsequent performance characterization is affected. The appearance of the acidified ABS powder is the same as that of the fluorescent powder, and the combination of functional groups is facilitated in a solvent, so that the grafting purpose is achieved. Thus, the acidified ABS powder was chosen for grafting.
The preparation method of the invention realizes the combination of the long afterglow luminescent material and the 3D printing technology through the means of organic modification and grafting. The prepared 3D printing composite material not only has the luminous property, but also improves the mechanical property, and greatly expands the application field of 3D printing. Can be further applied to the aspects of medicine, manufacturing industry, food industry, jewelry industry and the like.
Drawings
FIG. 1 is an XRD pattern for a long persistence phosphor, KH550 modified phosphor, and ABS grafted phosphor.
FIG. 2 is an infrared spectrum of a long afterglow phosphor, a KH550 modified phosphor, and KH 550.
FIG. 3 is an infrared spectrum of hydrochloric acid acidified ABS.
FIG. 4 is Sr 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ Infrared spectrogram grafted with ABS.
FIG. 5 is a graph comparing mechanical properties of ABS, 3D printed composites made in examples 1-3 and composites made in comparative examples 1-3.
Detailed Description
The invention is further described below with reference to the drawings and the detailed description.
Example 1
Strontium nitrate, magnesium nitrate, boric acid, tetraethoxysilane (TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the Respectively taking 1% of long afterglow fluorescent powder, 1% of KH550, 90% of ABS particles and 8% of ABS powder according to the mass percentage; dividing the ABS powder into two parts, wherein the mass of the first part of ABS powder is 1% of that of the ABS powder, and the mass of the second part of ABS powder is 99% of that of the ABS powder; adding 50mL deionized waterAdding KH550 into deionized water according to the proportion of 1mL, stirring for 5min, adding long afterglow fluorescent powder after hydrolysis reaction, refluxing at 80 ℃ for 10h (rotating speed of 250 r/min), naturally cooling to room temperature, centrifuging, filtering and washing with deionized water for multiple times, removing unreacted KH550, drying to constant weight at 80 ℃ in a vacuum drying oven, and grinding to obtain KH550 modified fluorescent powder; adding 1g of ABS powder into 50mL of hydrochloric acid, adding the first part of ABS powder into the hydrochloric acid, refluxing at 110 ℃ for 10h (rotating speed of 500 r/min), naturally cooling to room temperature, centrifuging, filtering and washing for multiple times by using ethanol and deionized water, drying at 80 ℃ in a vacuum drying oven to constant weight, and grinding to obtain acidified ABS; taking HATU according to the proportion that 1eq of HATU is needed for acidifying the ABS, completely dissolving the acidified ABS in DMF, adding the HATU, activating for 5min, adding fluorescent powder modified by KH550, stirring for 5h at room temperature (rotating speed 200 r/min), centrifuging, filtering and washing with deionized water for multiple times, drying to constant weight at 80 ℃ in a vacuum drying oven, and grinding to obtain ABS grafted fluorescent powder; uniformly mixing the ABS grafted fluorescent powder, the ABS particles and the second part of ABS powder to obtain a sustainable luminescent 3D printing blend; and (3) filling the blend into a 3D printing extruder for melt manufacturing, wherein the melt temperature is 245 ℃, and extruding, drawing and wire drawing are carried out to prepare the 3D printing ABS composite material capable of continuously emitting light.
Example 1 the 3D printed composite material was made as filaments having a diameter of about 1.75mm and a diameter error within + 0.03mm.
Comparative example 1
Strontium nitrate, magnesium nitrate, boric acid, tetraethoxysilane (TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the Respectively taking 1% of long afterglow fluorescent powder, 90% of ABS particles and 9% of ABS powder according to the mass percentage to obtain a blend; the blend was fed into a 3D printing extruder for melt fabrication at 245 ℃ to produce a first composite (ABS-1) by extrusion, drawing, wire drawing.
Example 2
Strontium nitrate, magnesium nitrate, boric acid and tetraethoxysilane(TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the According to the mass percentage, respectively taking 2% of long afterglow fluorescent powder, 2% of KH550, 89% of ABS particles and 7% of ABS powder, dividing the taken ABS powder into two parts, wherein the mass of the first part of ABS powder is 3% of that of the taken ABS powder, and the mass of the second part of ABS powder is 97% of that of the taken ABS powder; adding 3mL of KH550 into 50mL of deionized water, stirring for 10min, adding long-afterglow fluorescent powder after hydrolysis reaction, refluxing at 70 ℃ for 24h (rotating speed 500 r/min), naturally cooling to room temperature, centrifuging, filtering and washing with deionized water for multiple times to remove unreacted KH550, drying at 75 ℃ in a vacuum drying oven to constant weight, and grinding to obtain KH550 modified fluorescent powder; adding 5g of ABS powder into 50mL of hydrochloric acid, refluxing for 17h at 120 ℃, naturally cooling to room temperature, centrifuging, filtering and washing with ethanol and deionized water for multiple times, removing unreacted hydrochloric acid, drying in a vacuum drying oven at 70 ℃ to constant weight, and grinding to obtain acidified ABS; taking HATU according to the proportion of 1.3eq of HATU required for acidifying the ABS by 3g, dissolving the acidified ABS in DMF, adding the HATU, activating for 10min, adding the fluorescent powder modified by KH550, stirring for 3h at room temperature, centrifuging, filtering and washing with deionized water for multiple times, drying at 75 ℃ in a vacuum drying oven to constant weight, and grinding to obtain the ABS grafted fluorescent powder; uniformly mixing the ABS grafted fluorescent powder, the ABS particles and the second part of ABS powder to obtain a sustainable luminescent 3D printing blend; the blend is put into a 3D printing extruder for melt manufacturing, the melt temperature is 235 ℃, and the 3D printing ABS composite material capable of continuously emitting light is prepared through extrusion, traction and wire drawing.
Example 2 the 3D printed composite material was made as filaments having a diameter of about 1.75mm and a diameter error within + 0.03mm.
Comparative example 2
Strontium nitrate, magnesium nitrate, boric acid, tetraethoxysilane (TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the Respectively taking 2% of long afterglow fluorescent powder, 90% of ABS particles and 8% of ABS powder according to the mass percentage to obtain a blend; the blend was fed into a 3D printing extruder for melt fabrication at 235 c and extruded, drawn, and drawn to produce a first composite (ABS-2).
Example 3
Strontium nitrate, magnesium nitrate, boric acid, tetraethoxysilane (TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the Respectively taking 3% of long afterglow fluorescent powder, 3% of KH550, 88% of ABS particles and 6% of ABS powder according to the mass percentage; dividing the ABS powder into two parts, wherein the mass of the first part of ABS powder is 2% of that of the ABS powder, and the mass of the second part of ABS powder is 98% of that of the ABS powder; adding KH550 into 50mL deionized water according to the proportion of 2mL KH550, stirring for 8min, adding fluorescent powder after hydrolysis reaction, refluxing at 75 ℃ for 17h (rotating speed of 200 r/min), naturally cooling to room temperature, centrifuging, filtering and washing with deionized water for multiple times to remove unreacted KH550, drying at 70 ℃ in a vacuum drying oven to constant weight, and grinding to obtain KH550 modified fluorescent powder; adding 3g of ABS powder into 50mL of hydrochloric acid according to the proportion, adding the first part of ABS powder into the hydrochloric acid, refluxing for 24 hours at 115 ℃, naturally cooling to room temperature, centrifuging, filtering and washing for multiple times by using ethanol and deionized water, removing unreacted hydrochloric acid, drying to constant weight at 75 ℃ in a vacuum drying oven, and grinding to obtain acidified ABS; taking HATU according to the proportion of 1.1eq of HATU required for 2g of acidified ABS, completely dissolving the acidified ABS in N, N-dimethylformamide, adding the HATU, activating for 7min, adding KH550 modified fluorescent powder, stirring for 4h at room temperature, centrifuging, filtering and washing with deionized water for multiple times, drying at 70 ℃ in a vacuum drying box to constant weight, and grinding to obtain ABS grafted fluorescent powder; uniformly mixing the ABS grafted fluorescent powder, the ABS particles and the second part of ABS powder to obtain a sustainable luminescent 3D printing blend; the blend is put into a 3D printing extruder for melt manufacturing, and the melt temperature is highThe temperature is 250 ℃, and the 3D printing ABS composite material capable of continuously emitting light is prepared through extrusion, traction and wire drawing.
Example 1 the 3D printed composite material was made as filaments having a diameter of about 1.75mm and a diameter error within + 0.03mm.
Comparative example 3
Strontium nitrate, magnesium nitrate, boric acid, tetraethoxysilane (TEOS), europium oxide and dysprosium oxide are used as raw materials, and the long afterglow fluorescent powder (Sr) is prepared according to the preparation method in the prior art 2 MgSi 2 O 7 : Eu 2+ ,Dy 3+ ) The method comprises the steps of carrying out a first treatment on the surface of the Respectively taking 3% of long afterglow fluorescent powder, 90% of ABS particles and 7% of ABS powder according to the mass percentage to obtain a blend; the blend was fed into a 3D printing extruder for melt fabrication at a melt temperature of 250 ℃ to produce a first composite material (ABS-3) by extrusion, drawing, wire drawing.
As can be seen from the mechanical properties test chart shown in FIG. 5, the maximum tensile load of the material (ABS-0) made of 90% by mass of ABS particles and 10% by mass of ABS powder was 93.27N. The maximum tensile loads of the resulting hair composites ABS-1, ABS-2 and ABS-3 of comparative example 1, comparative example 2 and comparative example 3 were 74.1N, 67.21N and 56.58N, respectively. It can also be seen from FIG. 5 that the maximum tensile loads of ABS-1, ABS-2 and ABS-3 decrease with increasing doping levels of the long-afterglow phosphors, because the inherent stiffness of the inorganic filler (long-afterglow phosphor) has a great impact on the tensile properties of the composite. However, the maximum tensile loads of the sustainable luminescent 3D printed ABS composite ABS-1' (prepared in example 1), ABS-2' (prepared in example 2) and ABS-3' (prepared in example 3) grafted with KH550 modified long-afterglow phosphors were 83.42N, 85.43N and 85.51N, respectively, which are significantly improved compared to the maximum tensile loads of the composites (ABS-1, ABS-2 and ABS-3) prepared without KH550 treatment. This result also demonstrates that organic modification of the long persistence phosphor enhances the compatibility and dispersibility of the phosphor in ABS.
The KH550 modified grafted fluorescent powder and ABS are mechanically blended in an extrusion mode of an extruder, a two-phase staggered and interlocked co-continuous morphological structure can be formed in a molten state, certain phase interface affinity exists between the two components, the dispersion is uniform, the compatibility among the components is promoted, and the mechanical property of the composite material is improved.

Claims (4)

1. The preparation method of the sustainable luminescent 3D printing ABS composite material is characterized by comprising the following steps of:
1) According to the mass percentage, 1 to 3 percent of long afterglow fluorescent powder, (3-aminopropyl) triethoxysilane, 88 to 90 percent of ABS particles and 6 to 8 percent of ABS powder are respectively taken, and the total amount of each component is 100 percent; the long afterglow fluorescent powder is Sr 2 MgSi 2 O 7 Europium-dysprosium doped fluorescent powder; dividing the ABS powder into two parts, wherein the mass of the first part of ABS powder is 1-3% of that of the ABS powder, and the mass of the second part of ABS powder is 97-99% of that of the ABS powder;
2) Adding 1-3 mL (3-aminopropyl) triethoxysilane into 50mL deionized water, adding (3-aminopropyl) triethoxysilane into deionized water, hydrolyzing and stirring, adding long afterglow fluorescent powder, refluxing, naturally cooling to room temperature, centrifuging, filtering and washing, drying to constant weight, and grinding to obtain modified fluorescent powder;
3) Adding 1-5 g of ABS powder into 50mL of hydrochloric acid, adding the first part of ABS powder into the hydrochloric acid, refluxing, naturally cooling to room temperature, centrifuging, filtering, washing, drying to constant weight, and grinding to obtain acidified ABS;
4) Taking HATU according to the proportion that 1-1.3 eq of HATU is needed for acidifying the ABS, completely dissolving the acidified ABS in DMF, adding the HATU, activating, adding modified fluorescent powder, stirring at room temperature, centrifuging, filtering, washing, drying to constant weight, and grinding to obtain ABS grafted fluorescent powder;
5) Uniformly mixing the ABS grafted fluorescent powder, the ABS particles and the second part of ABS powder to obtain a sustainable luminescent 3D printing blend;
6) Loading the sustainable luminescent 3D printing blend into a 3D printing extruder for melt manufacturing, wherein the melt temperature is 235-250 ℃, and extruding, drawing and wiredrawing to prepare a sustainable luminescent 3D printing composite filament, namely the sustainable luminescent 3D printing ABS composite material;
the diameter of the 3D printing ABS composite material is 1.75+/-0.03 mm.
2. The method for preparing a sustainable luminescent 3D printed ABS composite according to claim 1 wherein the reflow in step 2): reflux is carried out for 10 to 24 hours at the temperature of between 70 and 80 ℃.
3. The method for preparing the sustainable luminescent 3D printing ABS composite according to claim 1 wherein the reflow in step 3): reflux is carried out for 10 to 24 hours at the temperature of 100 to 120 ℃.
4. The method for preparing a sustainable luminescent 3D printed ABS composite according to claim 1 wherein the drying in step 2), step 3) and step 4): and drying in a vacuum drying oven at 70-80 ℃ to constant weight.
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