CN108795011A - A kind of compound 3D printing fluorescent material of polymer ceramic and preparation method thereof - Google Patents
A kind of compound 3D printing fluorescent material of polymer ceramic and preparation method thereof Download PDFInfo
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- CN108795011A CN108795011A CN201810731613.0A CN201810731613A CN108795011A CN 108795011 A CN108795011 A CN 108795011A CN 201810731613 A CN201810731613 A CN 201810731613A CN 108795011 A CN108795011 A CN 108795011A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- 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
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Abstract
A kind of compound 3D printing fluorescent material of polymer ceramic of present invention offer and preparation method thereof, is related to 3D printing technique field, includes the constituent of following parts by weight：20-40 parts of SiC-TaC composite nano-powders,40-80 parts of PET resin,50-100 parts of polycarbonate resin,10-20 parts of high-density polyethylene resin,10-20 parts of PE-g-MAH,10-20 parts of styrene and butadiene block copolymer,10-20 parts of 0.1-0.2mm modified carbon fibers,5-10 parts of 0.4-0.6mm modified carbon fibers,5-10 parts of RC-HSt,1-5 parts of Fischer-Tropsch wax,1-5 parts of antioxidant,30-50 parts of rare-earth-doped strontium aluminate luminescent powder,The compound 3D printing material items excellent in mechanical performance of polymer ceramic of the present invention,Wearing coefficient is small,Wear-resisting property is high,Density is small,Luminous intensity is high,The shell of various engineering machinery can be made up of 3D printing technique,Construction material or toy for children,Market application prospect is extensive.
Description
Technical field
The present invention relates to 3D printing technique fields, and in particular to a kind of compound 3D printing fluorescent material of polymer ceramic and its
Preparation method.
Background technology
3D printing technique (also known as 3D rapid shaping techniques or increases material manufacturing technology) be start the late 1980s by
The new manufacture gradually risen.It refers under the control of the computer, according to CAD (CAD) mould of object
Type or computed tomography (CT) data are accumulated by the 3D of material, quickly manufacture the new of arbitrarily complicated shape 3D objects
Type digitizes forming technique.Its basic principle is " Layered manufacturing is successively superimposed ", passes through Computer Aided Design in a computer by one
(CAD) or tomoscan (CT) complete 3D solid part models, along space, a certain reference axis is divided into cuing open for specific thicknesses
Then face is printed in layer by printing device, then by section bonding, fusion, obtain required 3D objects.
For the more demanding of material, basic performance will be conducive to quickly and accurately process prototype zero 3D printing technique
Part meets some strength, rigidity and thermal stability requirement.To a certain extent, 3D printing material has become influence 3D printing
The key factor of future thrust, currently, 3D printing material includes mainly engineering plastics, photosensitive resin, metal, ceramic material
Material.
Each material has respective defect and advantage, made if complementation can be carried out in conjunction with two kinds of materials
3D printing material necessarily has and is more widely applied foreground, in addition, having had enterprise development to go out in the world a few days ago can be in dark
In send out the 3D printing wire rod of fluorescence, this also seldom report at home.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of compound 3D printing fluorescent material of polymer ceramic and its systems
Preparation Method.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
20-40 parts of composite granule of rice, 40-80 parts of PET resin, 50-100 parts of polycarbonate resin, high-density polyethylene resin 10-20
Part, 10-20 parts of PE-g-MAH, styrene and 10-20 parts of butadiene block copolymer, 0.1-0.2mm modified carbon fibers 10-20
Part, 5-10 parts of 0.4-0.6mm modified carbon fibers, 5-10 parts of RC-HSt, 1-5 parts of Fischer-Tropsch wax, 1-5 parts of antioxidant, rear-earth-doped aluminium
30-50 parts of sour strontium luminescent powder.
Preferably, include the constituent of following parts by weight：25-35 parts of SiC-TaC composite nano-powders, PET resin
50-70 parts, 60-90 parts of polycarbonate resin, 12-18 parts of high-density polyethylene resin, 12-18 parts of PE-g-MAH, styrene with
12-18 parts of butadiene block copolymer, 13-15 parts of 0.1-0.2mm modified carbon fibers, 6-8 parts of 0.4-0.6mm modified carbon fibers,
6-8 parts of RC-HSt, 1.5-4.5 parts of Fischer-Tropsch wax, 1.5-4.5 parts of antioxidant, 35-45 parts of rare-earth-doped strontium aluminate luminescent powder.
Preferably, include the constituent of following parts by weight：30 parts of SiC-TaC composite nano-powders, PET resin 55
Part, 80 parts of polycarbonate resin, 16 parts of high-density polyethylene resin, 15 parts of PE-g-MAH, styrene and butadiene block copolymer
16 parts of object, 14 parts of 0.1-0.2mm modified carbon fibers, 6.5 parts of 0.4-0.6mm modified carbon fibers, 7 parts of RC-HSt, 3 parts of Fischer-Tropsch wax,
2 parts of antioxidant, 40 parts of rare-earth-doped strontium aluminate luminescent powder.
Preferably, the preparation method of the SiC-TaC composite nano-powders is as follows：With tantalic chloride, ethyl orthosilicate and
Glucose is that raw material is prepared for glucose plural gel, and glucose plural gel obtains C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization
Presoma, C-SiO2-Ta2O5The grinding of hydridization presoma is placed in Ar atmosphere, and 1200-1500 DEG C of fabricated in situ obtains SiC-
TaC composite nano-powders.
Preferably, the contracting mould rate of the PET resin flow direction is 0.1-0.3%, and the contracting mould rate of vertical direction is 0.5-
0.8%.
Preferably, PE-g-MAH melt index (190 DEG C, 2.16Kg) the > 10g/10min.
Preferably, the 0.1-0.2mm modified carbon fibers, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：By two
The carbon fiber of kind specification is placed in 900 DEG C of Muffle furnace, after being passed through steam-activation treatment 1-2h, is taken out with 60 DEG C of leachings of the concentrated sulfuric acid
30-40min is steeped, taking-up is washed, dried, being placed in container, adds water, ethyl alcohol, silane coupling agent, is warming up to 40 DEG C, stirs 2-5h.
Preferably, water, ethyl alcohol, silane coupling agent mass ratio be 2:10:1.
Preferably, the antioxidant is any one or more combination in ZM-405, B900, XH245,1010.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260-270 DEG C, and screw rod turns
Speed is 60-80r/min, squeezes out batten cooling pelletization in air, and be dried in vacuo 5-10h in 140 DEG C, is obtained after crushing prefabricated
Object powder；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 280-300 DEG C, screw speed 100-120r/min, squeeze out batten, wire drawing
Molding, obtains finished product.
(3) advantageous effect
The present invention provides compound 3D printing fluorescent materials of a kind of polymer ceramic and preparation method thereof, have beneficial below
Effect：
SiC-TaC composite nano-powders have higher elasticity modulus, micro- hard compared to common ceramic powder in the present invention
Degree and high-temperature oxidation resistance are added as reinforced type ingredient, are combined with various kinds of resin, fully handed in the system of supercritical water
Fork connection, molecular resin are fully combined with SiC-TaC composite nano-powders, and 0.1-0.2mm modified carbon fibers and 0.4-0.6mm change
Property carbon fiber material bone and connection basic point, modified carbon fiber surface activity functional group number can be used as to increase, can be with
Preferably compatible with SiC-TaC composite nano-powders and organic resin material, the compound 3D printing of obtained polymer ceramic is glimmering
Luminescent material items excellent in mechanical performance, wearing coefficient is small, and wear-resisting property is high, and density is small, and luminous intensity is high, and fluorescent lifetime is long, can
The shell, construction material or toy for children of various engineering machinery to be made up of 3D printing technique, market application prospect is extensive.
And current ceramic material such as zirconium oxide, aluminium oxide, tricalcium phosphate, silicon carbide, carbon titanium silicide, ceramic forerunner etc.
3D printing can be achieved, method is usually used roller and paves ceramic powders in advance, and adhesive solution is then pressed part
Cross sectional shape is sprayed from nozzle, and powder bonding is made to form part shape together, is layering until molding the three of design
Dimension module needs to use adhesive in 3D printing, causes strength of parts limited since adhesive bonding strength is limited, it is difficult to obtain
The ceramic component of good mechanical performance is obtained, melt deposition forming technique can be used in the compound 3D printing material of polymer ceramic of the present invention
3D printing is carried out, so that the resin component in material is melted using the high temperature of liquefier, (insoluble powder and fiber uniformly disperse
In molten liquid), and then the mixture of melting is deposited on by syringe needle extrusion on platform by liquefier, can be obtained into after cooling
Product, mechanical strength is far above existing single ceramics or high molecule plastic 3D printing product.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
20-40 parts of composite granule of rice, 40-80 parts of PET resin, 50-100 parts of polycarbonate resin, high-density polyethylene resin 10-20
Part, 10-20 parts of PE-g-MAH, styrene and 10-20 parts of butadiene block copolymer, 0.1-0.2mm modified carbon fibers 10-20
Part, 5-10 parts of 0.4-0.6mm modified carbon fibers, 5-10 parts of RC-HSt, 1-5 parts of Fischer-Tropsch wax, 1-5 parts of antioxidant, rear-earth-doped aluminium
30-50 parts of sour strontium luminescent powder.
Further, include the constituent of following parts by weight：25-35 parts of SiC-TaC composite nano-powders, PET resin
50-70 parts, 60-90 parts of polycarbonate resin, 12-18 parts of high-density polyethylene resin, 12-18 parts of PE-g-MAH, styrene with
12-18 parts of butadiene block copolymer, 13-15 parts of 0.1-0.2mm modified carbon fibers, 6-8 parts of 0.4-0.6mm modified carbon fibers,
6-8 parts of RC-HSt, 1.5-4.5 parts of Fischer-Tropsch wax, 1.5-4.5 parts of antioxidant, 35-45 parts of rare-earth-doped strontium aluminate luminescent powder.
Further, include the constituent of following parts by weight：30 parts of SiC-TaC composite nano-powders, PET resin 55
Part, 80 parts of polycarbonate resin, 16 parts of high-density polyethylene resin, 15 parts of PE-g-MAH, styrene and butadiene block copolymer
16 parts of object, 14 parts of 0.1-0.2mm modified carbon fibers, 6.5 parts of 0.4-0.6mm modified carbon fibers, 7 parts of RC-HSt, 3 parts of Fischer-Tropsch wax,
2 parts of antioxidant, 40 parts of rare-earth-doped strontium aluminate luminescent powder.
Above-mentioned PET resin can be Dupont RE15030, RE19041, FC-51, FR-515, FR-530, FR-530-
The contracting mould rate of any one in BK, FR-543, FR-945, preferably Dupont FR-530, flow direction is 0.1-
0.3%, the contracting mould rate of vertical direction is 0.5-0.8%；
Above-mentioned polycarbonate resin is Japan Supreme Being people LV-2225Y or Bayer Bitterfeld GmbH 1803, preferably Japanese Supreme Being people LV-
2225Y；
Above-specified high density polyvinyl resin is Iran's petrochemical industry HD-EX5HDPE high density polyethylene (HDPE)s, Dow DGDO-
3364 high-density polyethylene resins, Taiwan plastic cement 8003H, preferably Taiwan plastic cement 8003H；
Above-mentioned PE-g-MAH is gold henry 9901, melt index (190 DEG C, 2.16Kg) > 10g/10min；
Above-mentioned styrene is high mountain SBS YH792 or YH791, preferably SBS YH792 with butadiene block copolymer；
Above-mentioned carbon fiber is that Shanghai power is large, specification 0.1-0.2mm, 0.4-0.6mm；
RC-HSt is consonance bio tech ltd's product；
Above-mentioned Fischer-Tropsch wax is import, the trade mark 105,105 DEG C of fusing point, maximum oil content 0.2%；
Above-mentioned rare-earth-doped strontium aluminate luminescent powder produces for Zhengzhou Han Shuo industrial chemicals Co., Ltd, and brand night is bright, type
Number L-7A.
The preparation method of the SiC-TaC composite nano-powders is as follows：It is with tantalic chloride, ethyl orthosilicate and glucose
Raw material is prepared for glucose plural gel, and glucose plural gel obtains C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization presoma,
C-SiO2-Ta2O5The grinding of hydridization presoma is placed in Ar atmosphere, 1200-1500 DEG C of fabricated in situ, obtains SiC-TaC nanometers again
Close powder.
Further, it uses TEOS for silicon source, it is mixed into (molar ratio with absolute ethyl alcohol, deionized water and dilute hydrochloric acid:
1:2:2:0.01) solution A, is obtained, with TaCl5It for tantalum source, is dissolved in excessive absolute ethyl alcohol, forms solution B；
It is mixed with solution B after solution A initial hydrolysis, stirs evenly instillation glucose solution, and micro dispersant is added
And coagulant, the aqueous povidone solution that dispersant is 1%, additive amount are 1% of water content in colloidal sol, coagulant is
Propylene oxide, after 3h, the mixed solution of A, B and C of sealing, which are statically placed in 60 DEG C of water-baths, makes it further hydrolyze, after 12h
To compound wet gel.After wet gel stands 3d, then through alcohol reflux to handle to obtain the composite dry containing carbon source and homogeneous transparent solidifying
Glue；
The composite xerogel block prepared is placed in mortar and is crushed, is then placed in the particle for being crushed to certain particle size
Carbonization, obtains the graininess C-SiO of black in 450 DEG C of Muffle furnace2-Ta2O5Hydridization presoma；
C-SiO2-Ta2O5Hydridization presoma is placed in Ar atmosphere, 1200-1500 DEG C of fabricated in situ, heating rate be 20 DEG C/
Min keeps the temperature 1h, obtains SiC-TaC composite nano-powders.
The 0.1-0.2mm modified carbon fibers, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：By two kinds of specifications
Carbon fiber be placed in 900 DEG C of Muffle furnace, after being passed through steam-activation treatment 1-2h, take out with 60 DEG C of concentrated sulfuric acid immersion 30-
40min, taking-up are washed, are dried, being placed in container, add water, ethyl alcohol, silane coupling agent, are warming up to 40 DEG C, stir 2-5h.
Water, ethyl alcohol, silane coupling agent mass ratio be 2:10:1, it is preferable that silane coupling agent KH550.
The antioxidant is any one or more combination in ZM-405, B900, XH245,1010.
The preparation method of the compound 3D printing fluorescent material of above-mentioned polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260-270 DEG C, and screw rod turns
Speed is 60-80r/min, squeezes out batten cooling pelletization in air, and be dried in vacuo 5-10h in 140 DEG C, is obtained after crushing prefabricated
Object powder；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, (water is 30MPa at this time
Supercriticality, supercritical water can activate high molecular material and it promoted at present may be used with the bonding of SiC-TaC composite nano-powders
To have been reported that, in 460 DEG C, 30min, supercritical water can control reaction condition with degradable PS, the present invention and both reach technology mesh
, and resin material is avoided to be degraded), restore normal temperature and pressure after reacting 5min；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 280-300 DEG C, screw speed 100-120r/min, squeeze out batten, wire drawing
Molding, obtains finished product.
Embodiment 1：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
30 parts of composite granule of rice, 55 parts of PET resin, 80 parts of polycarbonate resin, 16 parts of high-density polyethylene resin, PE-g-MAH 15
Part, styrene and 16 parts of butadiene block copolymer, 14 parts of 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers
6.5 parts, 7 parts of RC-HSt, 3 parts of Fischer-Tropsch wax, 2 parts of antioxidant, 40 parts of rare-earth-doped strontium aluminate luminescent powder.
The preparation method of the SiC-TaC composite nano-powders is as follows：It is with tantalic chloride, ethyl orthosilicate and glucose
Raw material is prepared for glucose plural gel, and glucose plural gel obtains C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization presoma,
C-SiO2-Ta2O5The grinding of hydridization presoma is placed in Ar atmosphere, and 1400 DEG C of fabricated in situ obtain SiC-TaC nano composite powders
Body.
The 0.1-0.2mm modified carbon fibers, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：By two kinds of specifications
Carbon fiber be placed in 900 DEG C of Muffle furnace, after being passed through steam-activation treatment 1-2h, take out with 60 DEG C of concentrated sulfuric acid immersion 30-
40min, taking-up are washed, are dried, being placed in container, add water, ethyl alcohol, silane coupling agent, are warming up to 40 DEG C, stir 2-5h.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260 DEG C, and screw speed is
70r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 8h in 140 DEG C, and preformed objects powder is obtained after crushing；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 290 DEG C, screw speed 110r/min, squeeze out batten, wire-drawing shape, obtain
To finished product.
Embodiment 2：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
25 parts of composite granule of rice, 50 parts of PET resin, 60 parts of polycarbonate resin, 12 parts of high-density polyethylene resin, PE-g-MAH 12
Part, styrene and 12 parts of butadiene block copolymer, 13 parts of 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers 6
Part, 6 parts of RC-HSt, 1.5 parts of Fischer-Tropsch wax, 1.5 parts of antioxidant, 35 parts of rare-earth-doped strontium aluminate luminescent powder.
The preparation method of the SiC-TaC composite nano-powders is as follows：It is with tantalic chloride, ethyl orthosilicate and glucose
Raw material is prepared for glucose plural gel, and glucose plural gel obtains C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization presoma,
C-SiO2-Ta2O5The grinding of hydridization presoma is placed in Ar atmosphere, and 1200 DEG C of fabricated in situ obtain SiC-TaC nano composite powders
Body.
The 0.1-0.2mm modified carbon fibers, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：By two kinds of specifications
Carbon fiber be placed in 900 DEG C of Muffle furnace, after being passed through steam-activation treatment 1-2h, take out with 60 DEG C of concentrated sulfuric acid immersion 30-
40min, taking-up are washed, are dried, being placed in container, add water, ethyl alcohol, silane coupling agent, are warming up to 40 DEG C, stir 2-5h.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260 DEG C, and screw speed is
60r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 5h in 140 DEG C, and preformed objects powder is obtained after crushing；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 280 DEG C, screw speed 100r/min, squeeze out batten, wire-drawing shape, obtain
To finished product.
Embodiment 3：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
35 parts of composite granule of rice, 70 parts of PET resin, 90 parts of polycarbonate resin, 18 parts of high-density polyethylene resin, PE-g-MAH 18
Part, styrene and 18 parts of butadiene block copolymer, 15 parts of 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers 8
Part, 8 parts of RC-HSt, 4.5 parts of Fischer-Tropsch wax, 4.5 parts of antioxidant, 45 parts of rare-earth-doped strontium aluminate luminescent powder.
The preparation method of the SiC-TaC composite nano-powders is as follows：It is with tantalic chloride, ethyl orthosilicate and glucose
Raw material is prepared for glucose plural gel, and glucose plural gel obtains C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization presoma,
C-SiO2-Ta2O5The grinding of hydridization presoma is placed in Ar atmosphere, and 1500 DEG C of fabricated in situ obtain SiC-TaC nano composite powders
Body.
The 0.1-0.2mm modified carbon fibers, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：By two kinds of specifications
Carbon fiber be placed in 900 DEG C of Muffle furnace, after being passed through steam-activation treatment 1-2h, take out with 60 DEG C of concentrated sulfuric acid immersion 30-
40min, taking-up are washed, are dried, being placed in container, add water, ethyl alcohol, silane coupling agent, are warming up to 40 DEG C, stir 2-5h.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 270 DEG C, and screw speed is
80r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 10h in 140 DEG C, and preformed objects powder is obtained after crushing；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 300 DEG C, screw speed 120r/min, squeeze out batten, wire-drawing shape, obtain
To finished product.
Embodiment 4：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
20 parts of composite granule of rice, 40 parts of PET resin, 50 parts of polycarbonate resin, 10 parts of high-density polyethylene resin, PE-g-MAH 10
Part, styrene and 10 parts of butadiene block copolymer, 10 parts of 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers 5
Part, 5 parts of RC-HSt, 1 part of Fischer-Tropsch wax, 1 part of antioxidant, 30 parts of rare-earth-doped strontium aluminate luminescent powder.
The preparation method of the SiC-TaC composite nano-powders is identical with embodiment 1.
Preparation method and the 1 complete phase of embodiment of the 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers
Together.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260 DEG C, and screw speed is
80r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 10h in 140 DEG C, and preformed objects powder is obtained after crushing；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 300 DEG C, screw speed 100r/min, squeeze out batten, wire-drawing shape, obtain
To finished product.
Embodiment 5：
A kind of compound 3D printing fluorescent material of polymer ceramic, includes the constituent of following parts by weight：SiC-TaC receives
40 parts of composite granule of rice, 80 parts of PET resin, 100 parts of polycarbonate resin, 20 parts of high-density polyethylene resin, PE-g-MAH 20
Part, styrene and 20 parts of butadiene block copolymer, 20 parts of 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers 10
Part, 10 parts of RC-HSt, 5 parts of Fischer-Tropsch wax, 5 parts of antioxidant, 50 parts of rare-earth-doped strontium aluminate luminescent powder.
The preparation method of the SiC-TaC composite nano-powders is identical with embodiment 1.
Preparation method and the 1 complete phase of embodiment of the 0.1-0.2mm modified carbon fibers, 0.4-0.6mm modified carbon fibers
Together.
The preparation method of the above-mentioned compound 3D printing fluorescent material of polymer ceramic, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene is embedding
Section copolymer, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260 DEG C, and screw speed is
65r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 6h in 140 DEG C, and preformed objects powder is obtained after crushing；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified
Carbon fiber is added in container, and water is added to stir, and container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts 5min
After restore normal temperature and pressure；
(4) it filters, will mix, be added to double with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material
Blending extrusion in screw extruder, blending temperature are 300 DEG C, screw speed 100r/min, squeeze out batten, wire-drawing shape, obtain
To finished product.
The compound 3D printing fluorescent material properties testing result of polymer ceramic prepared by 1-5 of the embodiment of the present invention is as follows
Shown in table 1：
Table 1：
Impact and tension test are pressed GB1804-79, ASTMD-256, GB1040-79 and are carried out respectively, instrument WPM-
Charpy types Apparatus for Impacting at low-temp, UJ-40IZOD types Apparatus for Impacting at low-temp and Shimadzu AG-200A type universal testing machines；
Wear-resisting property carries out on Germany's production SRV high temperature friction and wear testing machines, and specimen size is 10mm × 10mm, friction
Pair is ZrO2Ball, lubrication friction use machine oil as lubricant, test condition：Pressure 50N, vibration frequency 30Hz, amplitude 2mm, temperature
100 DEG C of degree；
Density is according to standard GB/T/T 1033.1-2008 plastics, non-foam plastic density assay method.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also include other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that：It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of compound 3D printing fluorescent material of polymer ceramic, which is characterized in that include the constituent of following parts by weight：
20-40 parts of SiC-TaC composite nano-powders, 40-80 parts of PET resin, 50-100 parts of polycarbonate resin, high density polyethylene (HDPE) tree
10-20 parts of 10-20 parts of fat, 10-20 parts of PE-g-MAH, styrene and butadiene block copolymer, 0.1-0.2mm are modified carbon fiber
It is 10-20 parts of dimension, 5-10 parts of 0.4-0.6mm modified carbon fibers, 5-10 parts of RC-HSt, 1-5 parts of Fischer-Tropsch wax, 1-5 parts of antioxidant, dilute
30-50 parts of native doped strontium aluminate luminescent powder.
2. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that including following parts by weight
Several constituents：25-35 parts of SiC-TaC composite nano-powders, 50-70 parts of PET resin, 60-90 parts of polycarbonate resin, height
12-18 parts of Density Polyethylene Resin, 12-18 parts of PE-g-MAH, styrene and 12-18 parts of butadiene block copolymer, 0.1-
13-15 parts of 0.2mm modified carbon fibers, 6-8 parts of 0.4-0.6mm modified carbon fibers, RC-HSt6-8 parts, 1.5-4.5 parts of Fischer-Tropsch wax,
1.5-4.5 parts of antioxidant, 35-45 parts of rare-earth-doped strontium aluminate luminescent powder.
3. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that including following parts by weight
Several constituents：30 parts of SiC-TaC composite nano-powders, 55 parts of PET resin, 80 parts of polycarbonate resin, high-density polyethylene
16 parts of olefine resin, 15 parts of PE-g-MAH, styrene and 16 parts of butadiene block copolymer, 0.1-0.2mm modified carbon fibers 14
Part, 6.5 parts of 0.4-0.6mm modified carbon fibers, 7 parts of RC-HSt, 3 parts of Fischer-Tropsch wax, 2 parts of antioxidant, rare-earth-doped strontium aluminate noctilucence
40 parts of powder.
4. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that the SiC-TaC receives
The preparation method of rice composite granule is as follows：It is compound it to be prepared for glucose using tantalic chloride, ethyl orthosilicate and glucose as raw material
Gel, glucose plural gel obtain C-SiO in 450 DEG C of calcinings2-Ta2O5Hydridization presoma, C-SiO2-Ta2O5Hydridization presoma
Grinding is placed in Ar atmosphere, and 1200-1500 DEG C of fabricated in situ obtains SiC-TaC composite nano-powders.
5. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that the PET resin stream
The contracting mould rate in dynamic direction is 0.1-0.3%, and the contracting mould rate of vertical direction is 0.5-0.8%.
6. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that the PE-g-MAH is molten
Melt index (190 DEG C, 2.16Kg) > 10g/10min.
7. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that the 0.1-0.2mm
Modified carbon fiber, the preparation method of 0.4-0.6mm modified carbon fibers are as follows：The carbon fiber of two kinds of specifications is placed in 900 DEG C of horse
Not in stove, after being passed through steam-activation treatment 1-2h, takes out and impregnate 30-40min for 60 DEG C with the concentrated sulfuric acid, taking-up is washed, dried, setting
In container, add water, ethyl alcohol, silane coupling agent, be warming up to 40 DEG C, stirs 2-5h.
8. the compound 3D printing fluorescent material of polymer ceramic as claimed in claim 8, which is characterized in that water, ethyl alcohol, silane are even
The mass ratio for joining agent is 2:10:1.
9. the compound 3D printing fluorescent material of polymer ceramic as described in claim 1, which is characterized in that the antioxidant is
Any one or more combination in ZM-405, B900, XH245,1010.
10. the preparation method of the compound 3D printing fluorescent material of polymer ceramic as claimed in any one of claims 1-9 wherein, special
Sign is, includes the following steps：
(1) material of above-mentioned parts by weight is weighed；
(2) PET resin, polycarbonate resin, high-density polyethylene resin, PE-g-MAH, styrene and butadiene block are total to
Polymers, RC-HSt, Fischer-Tropsch wax are added to blending extrusion in double screw extruder, and blending temperature is 260-270 DEG C, and screw speed is
60-80r/min squeezes out batten cooling pelletization in air, and is dried in vacuo 5-10h in 140 DEG C, and preformed objects powder is obtained after crushing
End；
(3) preformed objects powder, SiC-TaC composite nano-powders, 0.1-0.2mm modified carbon fibers, 0.4-0.6mm are modified carbon fiber
Dimension is added in container, adds water to stir, container is placed in overcritical device, is warming up to 380 DEG C, 30MPa, reacts extensive after 5min
Multiple normal temperature and pressure；
(4) it filters, will be mixed with rare-earth-doped strontium aluminate luminescent powder, antioxidant after 100 DEG C of drying of solid material, be added to twin-screw
Blending extrusion in extruder, blending temperature be 280-300 DEG C, screw speed 100-120r/min, squeeze out batten, wire drawing at
Type obtains finished product.
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| CN116177995A (en) * | 2022-09-07 | 2023-05-30 | 中国科学院上海硅酸盐研究所 | Preparation method of fluorescent ceramic based on 3D printing composite structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651791A (en) * | 2018-12-04 | 2019-04-19 | 上海市机械施工集团有限公司 | 3D printing fluorescence modified polycarbonate composite material and preparation method and application |
| CN109651791B (en) * | 2018-12-04 | 2020-12-25 | 上海市机械施工集团有限公司 | Fluorescent modified polycarbonate composite material for 3D printing and preparation method and application thereof |
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| CN116177995B (en) * | 2022-09-07 | 2024-03-12 | 中国科学院上海硅酸盐研究所 | Preparation method of fluorescent ceramic based on 3D printing composite structure |
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