CN110394192A - A kind of light of 3D printing skeleton@zinc oxide urges the preparation method of device - Google Patents
A kind of light of 3D printing skeleton@zinc oxide urges the preparation method of device Download PDFInfo
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- CN110394192A CN110394192A CN201910657588.0A CN201910657588A CN110394192A CN 110394192 A CN110394192 A CN 110394192A CN 201910657588 A CN201910657588 A CN 201910657588A CN 110394192 A CN110394192 A CN 110394192A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 66
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007639 printing Methods 0.000 claims description 7
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 6
- 241000196252 Ulva Species 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 235000016425 Arthrospira platensis Nutrition 0.000 claims description 2
- 240000002900 Arthrospira platensis Species 0.000 claims description 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229940082787 spirulina Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000001125 extrusion Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Robotics (AREA)
- Inorganic Chemistry (AREA)
Abstract
The light that the present invention discloses a kind of 3D printing skeleton zinc oxide urges the preparation method of device, is made by following methods: (1) preparing the heat-resisting profile and wire containing biomass, obtain different structure skeleton product by 3D printing (FDM)；(2) in 3D printing skeleton surface hydrothermal synthesis zinc oxide.The advantages that light of the invention urges device, there is light to urge high-efficient, is easily recycled, and cost is relatively low, and preparation process is simple.It can be applied to the photocatalytic degradation processing of sewage, air and organic contaminants in soil.
Description
Technical field
The invention belongs to waste water, the environment protection field of exhaust-gas treatment, and in particular to a kind of light of 3D printing skeleton@zinc oxide is urged
The preparation method of device.
Background technique
As process of industrialization quickly propels, the development model of the economic light environmental protection of weight causes the rings such as atmosphere, water body, soil
Border pollution problem.These problems bring significant challenge to the sustainable development of human society, and solving environmental problem has been to carve not allowing
It is slow.Wherein water pollution is an extremely important link.There are many water pollution processing method, and wherein photocatalysis technology is a kind of benefit
The effective ways of problem of environmental pollution are solved with new energy, it utilizes photocatalytic degradation poisonous and harmful substance, provides one kind
Very environment protection treating pollution method.But most of photochemical catalyst is powder at present, hardly possible, which recycles, becomes limit its application one greatly
Problem, device are then the feasible methods for solving this problem.
Realize that there are many device method, are such as coated in a variety of materials surface, CN201510118618.2 for catalyst at present
Disclose the preparation method and coating method of two kinds of coating agent of photocatalysis with CN201510118543.8, this method load factor compared with
Height, but complex and immobilized catalyst is easy to fall off.Also have and various photocatalysis are made with the direct melt blending of high molecular material
Material, this method is relatively simple, but catalyst is largely coated on inside macromolecule, causes to waste.
3D printing is a kind of novel intelligent increases material manufacturing technology, is compared compared to traditional molding mode, have quickly preparation,
The advantages that fining manufacture, stock utilization height, product structure can design.Wherein fused glass pellet (FDM) is popularized the most
3D printing technique, high molecular material can be printed as the device of labyrinth by it, to meet the different demands of different application.
Hydro-thermal reaction carries out generally in hydrothermal reaction kettle, and hydrothermal reaction kettle is the spontaneous means of press seals pressure vessel that is heated.Water
Thermal synthesis technology be it is a kind of react mild, easily-controllable, energy saving and of low pollution new synthesis route, have valence stabilityization effect with it is non-
Oxygen is embedded in the features such as feature.
If 3D printing device can be combined with photocatalytic degradation, it will expansion 3D printing application range significantly.This hair
It is bright to be combined by 3D printing technique with hydrothermal technique, realize immobilization of the photochemical catalyst on 3D printing product.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of light of 3D printing skeleton@zinc oxide to urge device
Preparation method.
Matrix resin selected by the present invention is a kind of material with excellent mechanical performance, heat resistance and machinability,
It is the mainstay material of 3D printing (FDM).Present invention introduces a kind of small unicellular autotrophs of volume, rich in functional function
Group can make 3D printing device surface more easily loading ZnO, manufacture the 3D printing line containing biomass by twin screw extrusion process
Material makes 3D printing device keep its original shape in light-catalyst ZnO synthesis process using heat-resist resin as matrix
Looks.
Light-catalyst ZnO of the present invention is synthesized by the method for hydro-thermal, and 3D is added in ZnO hydro-thermal method synthesis process and beats
Part is printed, realizes the purpose for being carried on 3D product.ZnO hydrothermal synthesis temperature is 100~200 DEG C, and reaction temperature is lower, is closed
At not will cause in the process the aging of 3D printing product matrix resin, degradation.Compared with melt-blending process, it is able to solve photochemical catalyst
With catalysis material made of the direct melt blending of high molecular material, most of photocatalysis auxiliary agent is coated on inside macromolecule, makes
The problems such as at waste.Compared with the precipitation method directly load, it is able to solve that photochemical catalyst is poor, easy to fall off with basal body binding force to ask
Topic.
In order to realize that the present invention, specific technical solution are as follows:
A kind of light of 3D printing skeleton@zinc oxide urges the preparation method of device, which comprises the following steps:
(1) 59-91 parts of matrix resin, 8-40 parts of biomass, 0.05-2 parts of white oil are placed in high-speed kneading machine, keep revolving speed
Put into screw extruder after 1000-6000rpm, high-speed stirred 5-20min, 160-255 DEG C of processing temperature, screw speed 80-
280rpm, extruding pelletization obtain master batch and squeeze out through wire rod machine, draw, are wound into wire rod, obtain skin-core structure 3D printing wire rod,
The 3D printing skeleton of controlled shape is obtained with 3D printing again；
(2) uniform hydrolyses in deionized water are added in zinc salt and organic acid, instill aqueous slkali under the stirring of 10-80r/min rate
PH=8-10 is adjusted, obtained suspension is ultrasonically treated at 25-60kHz；
(3) hydrothermal reaction kettle is added in suspension obtained in 3D printing skeleton obtained in step (1) and step (2) simultaneously
In, 18~36h of confined reaction in 100~200 DEG C of environment is rinsed, dries after reaction, obtains 3D printing skeleton@
The light of zinc oxide urges device.
Matrix resin in the step (1), selected from one or more of ABS, ASA, PPS, POM, PC, PEEK, PA.
Biomass in the step (1) is selected from one or more of chlorella, Enteromorpha, spirulina, algae-residue.
Matrix resin and biomass are dried in vacuo 8-12h respectively in the step (1).
3D printing condition in above-mentioned steps (1) are as follows: print temperature is 180-250 DEG C, baseplate temp is 50-100 DEG C, beats
Print-out rate is 20-150mm/s, printing thickness is 0.1-0.4mm.
In above-mentioned steps (2) ZnO hydro-thermal method synthesis in zinc salt, organic acid, water mass ratio are as follows: 1:1.5:60；It is described
Zinc salt in step (2) are as follows: one of zinc acetate, zinc nitrate, zinc sulfate；Step (3) organic acid are as follows: oxalic acid, citric acid
One of；The instillation rate of aqueous slkali in the step (2) are as follows: 10-20mL/min.
3D printing skeleton obtained in step (1) and suspension vol ratio obtained in step (2) in above-mentioned steps (3)
Are as follows: 0.01-0.05:1.
After adopting the above technical scheme, can be made into labyrinth the invention has the following beneficial effects: 1, preparation method is simple and efficient
Photocatalytic device；2, biomass provides active site for device surface, and a large amount of photochemical catalysts is made to be evenly distributed in device table
Face；3, matrix selects heat resistant type resin, is conducive to protect 3D device architecture during hydrothermal synthesis light urges agent ZnO, improves light
Urge device service life.
Detailed description of the invention
Fig. 1 is 20 four sides conveyor screw of 3D printing model；
Fig. 2 is the surface topography that device is urged using the light of 3D printing skeleton@zinc oxide prepared by the embodiment of the present invention 1；
Fig. 3 is to urge device using the light of 3D printing skeleton@zinc oxide prepared by the embodiment of the present invention 1, is dropped to the light of rhodamine B
Solution and dark adsorption activity spectrogram.
Specific embodiment
Embodiment 1
It is to sequentially include the following steps: that a kind of light of 3D printing skeleton@zinc oxide, which urges the preparation method of device,
(1) ABS, chlorella are dried in vacuo 12h, ABS (700g), chlorella (299.5g) and the white oil after weighing drying
(0.5g), is placed in high-speed kneading machine, keeps revolving speed 1000rpm, puts into double screw extruder after high-speed stirred 5min, squeezes out
Temperature is set as 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 190 DEG C, 185 DEG C, 170 DEG C, 165 DEG C, in double spiral shells
Bar melts intracavitary fusion plastification and with revolving speed for 150rpm, squeezes out raw material, and the lines of head extrusion are entered to the sink for having cold water,
Abundant cooling by water；Lines enter dragger winding, obtain 3D printing wire rod.
(2) by above-mentioned wire rod, being printed as volume by 3D printer (FDM) is 1cm320 four sides conveyor screws (see figure
1), 3D printer parameter are as follows: print temperature is 185 DEG C, baseplate temp is 60 DEG C, print speed 50mm/s, printing thickness are
0.1mm。
(3) uniform hydrolyses in 60mL deionized water are added in zinc acetate 0.8g and citric acid 1.0g, instilled under stiring
1mol/L NaOH solution is adjusted to PH=9, mixing speed are as follows: 25r/min, the instillation rate of NaOH solution are as follows: 20mL/min, it will
The suspension finally obtained moves into ultrasonic container, and 45Hz is ultrasonically treated 1h.
(4) suspension will be obtained in 20 four sides conveyor screw small cube of 3D printing and step (3) that step (2) obtains
80mL is added in 100mL hydrothermal reaction kettle simultaneously, and confined reaction is for 24 hours in 120 DEG C of environment.3D printing photocatalysis is taken out after reaction
Device rinses 3 times with deionization and is rinsed 3 times with dehydrated alcohol again, finally dried for 24 hours at 25 DEG C.
(5) device is urged (to urge device see the light that Fig. 2 is 3D printing skeleton@zinc oxide the light of gained 3D printing skeleton@zinc oxide
The surface topography of part) it is added in the rhodamine B solution that 80mL concentration is 30mg/L, being protected from light stirring 120min makes to reach absorption
After desorption equilibrium, it is that light source carries out illumination with ultraviolet light (500W), samples, distinguished with ultraviolet specrophotometer at regular intervals
Measure absorbance.It obtains and urges device to rhodamine B using the light of 3D printing skeleton@zinc oxide prepared by the embodiment of the present invention 1
Light degradation and dark adsorption activity spectrogram (see figure 3).
Embodiment 2
It is to sequentially include the following steps: that a kind of light of 3D printing skeleton@zinc oxide, which urges the preparation method of device,
(1) ASA, Enteromorpha are dried in vacuo 12h, ASA (780g), Enteromorpha (218g) and the white oil (2g) after weighing drying are placed in
In high-speed kneading machine, revolving speed 1000rpm is kept, puts into double screw extruder after high-speed stirred 5min, extrusion temperature is set as
160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 190 DEG C, 185 DEG C, 170 DEG C, 165 DEG C melt intracavitary molten in twin-screw
Melt plasticizing and with revolving speed for 150rpm, squeeze out raw material, the lines of head extrusion are entered to the sink for having cold water, abundant water cooling is cold
But；Lines enter dragger winding, obtain 3D printing wire rod.
(2) by above-mentioned wire rod, being printed as volume by 3D printer (FDM) is 1cm320 four sides conveyor screws (Fig. 1),
3D printer parameter are as follows: print temperature is 190 DEG C, baseplate temp is 60 DEG C, print speed 50mm/s, printing thickness are
0.2mm。
(3) uniform hydrolyses in 50mL deionized water are added in zinc sulfate 1.0g and oxalic acid 2.3g, instill 1mol/ under stiring
L NaOH solution is adjusted to PH=8, mixing speed are as follows: 25r/min, the instillation rate of NaOH solution are as follows: 15mL/min, it will be final
The suspension of acquisition moves into ultrasonic container, and 45Hz is ultrasonically treated 30min.
(4) suspension will be obtained in 20 four sides conveyor screw small cube of 3D printing and step (3) that step (2) obtains
80mL is added in 100mL hydrothermal reaction kettle simultaneously, and confined reaction is for 24 hours in 120 DEG C of environment.3D printing photocatalysis is taken out after reaction
Device rinses 3 times with deionization and is rinsed 3 times with dehydrated alcohol again, 12h is finally dried at 25 DEG C.
Embodiment 3
It is to sequentially include the following steps: that a kind of light of 3D printing skeleton@zinc oxide, which urges the preparation method of device,
(1) PA, algae-residue are dried in vacuo 12h, PA (650g), algae-residue (347g) and the white oil (3g) after weighing drying are placed in height
In fast kneader, revolving speed 1000rpm is kept, puts into double screw extruder after high-speed stirred 5min, extrusion temperature is set as 170
DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 205 DEG C, 205 DEG C, 195 DEG C, 185 DEG C, 170 DEG C, 165 DEG C, melt intracavitary melting modeling in twin-screw
Change and be 150rpm with revolving speed, squeeze out raw material, the lines of head extrusion are entered to the sink for having cold water, abundant cooling by water；
Lines enter dragger winding, obtain 3D printing wire rod.
(2) by above-mentioned wire rod, being printed as volume by 3D printer (FDM) is 1cm320 four sides conveyor screws (Fig. 1),
3D printer parameter are as follows: print temperature is 195 DEG C, baseplate temp is 60 DEG C, print speed 50mm/s, printing thickness are
0.1mm。
(3) uniform hydrolyses in 60mL deionized water are added in zinc nitrate 1.5g and citric acid 2.0g, instilled under stiring
1mol/L NaOH solution is adjusted to PH=9, mixing speed are as follows: 25r/min, the instillation rate of NaOH solution are as follows: 20mL/min, it will
The suspension finally obtained moves into ultrasonic container, and 45Hz is ultrasonically treated 1h.
(4) suspension will be obtained in 20 four sides conveyor screw small cube of 3D printing and step (3) that step (2) obtains
80mL is added in 100mL hydrothermal reaction kettle simultaneously, and confined reaction is for 24 hours in 120 DEG C of environment.3D printing photocatalysis is taken out after reaction
Device rinses 3 times with deionization and is rinsed 3 times with dehydrated alcohol again, 18h is finally dried at 25 DEG C.
Embodiment 4
It is to sequentially include the following steps: that a kind of light of 3D printing skeleton@zinc oxide, which urges the preparation method of device,
(1) PA, chlorella are dried in vacuo 12h, PA (650g), chlorella (347g) and the white oil (3g) after weighing drying are set
In high-speed kneading machine, revolving speed 1000rpm is kept, double screw extruder, extrusion temperature setting are put into after high-speed stirred 5min
For 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 205 DEG C, 205 DEG C, 195 DEG C, 185 DEG C, 170 DEG C, 165 DEG C, melted in twin-screw intracavitary
Fusion plastification and be 150rpm with revolving speed squeezes out raw material, and the lines of head extrusion are entered to the sink for having cold water, abundant water cooling
It is cooling；Lines enter dragger winding, obtain 3D printing wire rod.
(2) by above-mentioned wire rod, being printed as volume by 3D printer (FDM) is 1cm320 four sides conveyor screws (Fig. 1),
3D printer parameter are as follows: print temperature is 195 DEG C, baseplate temp is 60 DEG C, print speed 50mm/s, printing thickness are
0.1mm。
(3) uniform hydrolyses in 50mL deionized water are added in zinc sulfate 1.0g and oxalic acid 2.3g, instill 1mol/ under stiring
L NaOH solution is adjusted to PH=8, mixing speed are as follows: 25r/min, the instillation rate of NaOH solution are as follows: 15mL/min, it will be final
The suspension of acquisition moves into ultrasonic container, and 45Hz is ultrasonically treated 30min.
(4) suspension will be obtained in 20 four sides conveyor screw small cube of 3D printing and step (3) that step (2) obtains
80mL is added in 100mL hydrothermal reaction kettle simultaneously, and confined reaction is for 24 hours in 120 DEG C of environment.3D printing photocatalysis is taken out after reaction
Device rinses 3 times with deionization and is rinsed 3 times with dehydrated alcohol again, 12h is finally dried at 25 DEG C.
Embodiment 5
It is to sequentially include the following steps: that a kind of light of 3D printing skeleton@zinc oxide, which urges the preparation method of device,
(1) POM, Enteromorpha are dried in vacuo 12h, ABS (700g), Enteromorpha (299.5g) and the white oil (0.5g) after weighing drying,
It is placed in high-speed kneading machine, keeps revolving speed 1000rpm, put into double screw extruder after high-speed stirred 5min, extrusion temperature is set
It is set to 160 DEG C, 170 DEG C, 1705 DEG C, 175 DEG C, 185 DEG C, 185 DEG C, 180 DEG C, 180 DEG C, 170 DEG C, 165 DEG C, melts chamber in twin-screw
Interior fusion plastification and be 150rpm with revolving speed squeezes out raw material, and the lines of head extrusion are entered to the sink for having cold water, abundant water
Cooling；Lines enter dragger winding, obtain 3D printing wire rod.
(2) by above-mentioned tool wire rod, being printed as volume by 3D printer (FDM) is 1cm320 four sides conveyor screws (figure
1), 3D printer parameter are as follows: print temperature is 185 DEG C, baseplate temp is 60 DEG C, print speed 50mm/s, printing thickness are
0.1mm。
(3) uniform hydrolyses in 60mL deionized water are added in zinc nitrate 1.5g and citric acid 2.0g, instilled under stiring
1mol/L NaOH solution is adjusted to PH=9, mixing speed are as follows: 25r/min, the instillation rate of NaOH solution are as follows: 15mL/min, it will
The suspension finally obtained moves into ultrasonic container, and 45Hz is ultrasonically treated 1h.
(4) suspension will be obtained in 20 four sides conveyor screw small cube of 3D printing and step (3) that step (2) obtains
80mL is added in 100mL hydrothermal reaction kettle simultaneously, and confined reaction is for 24 hours in 120 DEG C of environment.3D printing photocatalysis is taken out after reaction
Device rinses 3 times with deionization and is rinsed 3 times with dehydrated alcohol again, finally dried for 24 hours at 25 DEG C.
Claims (7)
1. the preparation method that a kind of light of 3D printing skeleton@zinc oxide urges device, which comprises the following steps:
(1) 59-91 parts of matrix resin, 8-40 parts of biomass, 0.05-2 parts of white oil are placed in high-speed kneading machine, keep revolving speed
Put into screw extruder after 1000-6000rpm, high-speed stirred 5-20min, 160-255 DEG C of processing temperature, screw speed 80-
280rpm, extruding pelletization obtain master batch and squeeze out through wire rod machine, draw, are wound into wire rod, obtain skin-core structure 3D printing wire rod,
The 3D printing skeleton of controlled shape is obtained with 3D printing again；
(2) uniform hydrolyses in deionized water are added in zinc salt and organic acid, instill aqueous slkali under the stirring of 10-80r/min rate
PH=8-10 is adjusted, obtained suspension is ultrasonically treated at 25-60kHz；
(3) hydrothermal reaction kettle is added in suspension obtained in 3D printing skeleton obtained in step (1) and step (2) simultaneously
In, 18~36h of confined reaction in 100~200 DEG C of environment is rinsed, dries after reaction, obtains 3D printing skeleton@
The light of zinc oxide urges device.
2. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In matrix resin in the step (1), selected from one or more of ABS, ASA, PPS, POM, PC, PEEK, PA.
3. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In biomass in the step (1) is selected from one or more of chlorella, Enteromorpha, spirulina, algae-residue.
4. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In matrix resin and biomass are dried in vacuo 8-12h respectively in the step (1).
5. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In 3D printing condition in step (1) are as follows: print temperature is 180-250 DEG C, baseplate temp is 50-100 DEG C, print speed is
20-150mm/s, printing thickness are 0.1-0.4mm.
6. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In, in step (2) ZnO hydro-thermal method synthesis in zinc salt, organic acid, water mass ratio are as follows: 1:1.5:60；In the step (2)
Zinc salt are as follows: one of zinc acetate, zinc nitrate, zinc sulfate；Step (3) organic acid are as follows: one of oxalic acid, citric acid；
The instillation rate of aqueous slkali in the step (2) are as follows: 10-20mL/min.
7. a kind of light of 3D printing skeleton@zinc oxide according to claim 1 urges the preparation method of device, feature exists
In 3D printing skeleton obtained in step (1) and suspension vol ratio obtained in step (2) in step (3) are as follows: 0.01-
0.05:1。
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