CN111645224B - Preparation method of 3D printing self-suspension photocatalytic device - Google Patents

Preparation method of 3D printing self-suspension photocatalytic device Download PDF

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CN111645224B
CN111645224B CN202010556394.4A CN202010556394A CN111645224B CN 111645224 B CN111645224 B CN 111645224B CN 202010556394 A CN202010556394 A CN 202010556394A CN 111645224 B CN111645224 B CN 111645224B
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CN111645224A (en
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薛珲
毛婧芸
夏新曙
钱庆荣
郑荧炼
刘欣萍
曾令兴
罗永晋
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Fujian Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment
    • 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
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • 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
    • 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

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Abstract

The invention discloses a preparation method of a 3D printing self-suspension photocatalytic device, and a photocatalyst is loaded on a sheet material through a thermal deposition method. The method comprises the following steps: after wires are extruded by a double-screw extruder and a single-screw extruder, the wires are printed into thin sheets with holes by using a 3D printing technology, and the photocatalyst is loaded on the thin sheets by using a thermal deposition method. The method is suitable for photocatalytic degradation of pollutants and photolysis of water to produce hydrogen and oxygen. The invention utilizes the glass transition temperature of the sheet material to ensure that the catalyst can be firmly loaded on the sheet material. The density of the sheet material can be adjusted to enable the sheet material to be suspended on the liquid surface, so that the catalyst can effectively utilize light, and the difficulties that the suspension liquid in a photocatalytic system has high turbidity, the photocatalyst is difficult to recover and recycle and the like are solved.

Description

Preparation method of 3D printing self-suspension photocatalytic device
Technical Field
The invention belongs to the field of application of photocatalysis technology, and particularly relates to a preparation method of a 3D printing self-suspension photocatalyst.
Background
Environmental pollution and energy exhaustion are important issues facing and urgently awaiting solution for human beings. The semiconductor photocatalysis technology is considered to be an ideal environmental pollution treatment technology due to the uniqueness that the semiconductor photocatalysis technology can directly utilize sunlight, can react at normal temperature, has no secondary pollution and the like. Moreover, the direct conversion from solar energy to hydrogen energy is realized by decomposing water to prepare hydrogen by photocatalysis, and the method is an ideal way for obtaining new energy. At present, photocatalysis is used as an effective means for converting light energy into chemical energy, and can be widely applied to the fields of photocatalytic degradation of pollutants, hydrogen production and oxygen production by water photolysis and the like. However, most of the existing photocatalysts are powder, and have the problems of low light utilization rate, difficult recovery, high recovery cost and the like. Therefore, the device formation of the photocatalyst is of great significance.
3D printing is used as an additive manufacturing technology, and has the characteristics of customization, various consumables and the like; ABS as a common 3D printing consumable has the characteristics of heat resistance, impact resistance, low temperature resistance, chemical resistance and the like, has a stable structure, is not easily influenced by sunlight, is difficult to degrade and has good stability. The traditional ABS consumables have the problem that printing is easy to warp, so that other polymers are used for modifying the traditional ABS consumables so as to be suitable for catalyst device formation.
If the device is to be suspended on a liquid surface, it is sufficient that the buoyancy to which the device is subjected is similar to the weight of the device, i.e. the overall density of the device is approximately equal to the density of the liquid. By designing the device, controlling wall thickness and volume, taking into account resin density, according to
Figure DEST_PATH_IMAGE002
And calculating the overall density of the device, so that the designed overall density of the device is approximately equal to the density of the liquid, and the device has a self-suspension effect. For example: ABS/PC resin is used as the outer wall of the model, water-soluble PVA is used as the filling layer, a rectangular sheet with the specification size of 10 multiplied by 0.36 cm and the wall thickness of 0.16 cm is printed by a double-nozzle printer, and the density of the ABS/PC resin is about 1.11 g/cm3Then the required mass of ABS/PC resin is about 35.91 g, the internal filling layerPrinted by PVA, the filling layer is dissolved by water after the printing is finished, and the overall density of the obtained device is about 0.99 g/cm3The density of the device is similar to that of water, and the effect that the device is suspended in the water body can be achieved.
Disclosure of Invention
The invention aims to overcome the difficulties of difficult recovery, low repeated utilization rate and low light utilization rate of the traditional photocatalyst, ensure that the performance of the immobilized catalyst is superior to that of a powder catalyst and the stability is excellent, control the density of the sheet by adjusting the proportion of raw materials, the shape of the sheet and the number of holes, ensure that the sheet is suspended in the liquid level, shorten the distance between a light source and the catalyst, improve the light utilization rate, and be favorable for improving the utilization rate of the catalyst by loading the catalyst on the surface of the sheet, thereby providing a preparation method for realizing catalyst device.
The invention discloses a preparation method of a 3D printing self-suspension photocatalytic device, which adopts the following technical scheme:
a preparation method of a 3D printing self-suspension photocatalytic device is characterized by comprising the following steps:
1) uniformly mixing ABS and modified resin according to the proportion of 70-85: 15-30 by a high-speed mixer, carrying out melt blending by a double-screw extruder, and carrying out extrusion granulation to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single screw extruder, cooling the extruded filament by water, and drawing and controlling the wire diameter by a drawing machine to prepare a wire with the wire diameter of 1.75 +/-0.05 mm;
3) through model design, printing the outer wall of the model by the wire obtained in the step 2), printing the inner filling of the model by the water-soluble PVA wire, and reserving 2-6 holes in the model, wherein the hole diameter is 0.2-0.6 cm;
4) dispersing 0.4-1.5 wt% of photocatalyst in isopropanol, placing the device obtained in the step 3) and the isopropanol according to the volume ratio of less than 1: 1-1: 10 after ultrasonic dispersion, naturally airing, and placing in an oven for heat treatment at 130-170 ℃ for 5-30 min;
5) and (3) putting the device obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 hour, washing with the deionized water for 4-6 times to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60-80 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
The modified resin is selected from one or more of thermoplastic polyurethane elastomer rubber (TPU), thermoplastic elastomer (TPE), acrylonitrile-styrene copolymer (SAN), Polycarbonate (PC) and polyamide-6 (PA 6).
The parameters of the double-screw extruder are as follows: the first zone is 85-135 ℃, the second zone is 115-165 ℃, the third zone is 135-180 ℃, the fourth zone is 150-195 ℃, the fifth zone is 160-210 ℃, the sixth zone is 170-230 ℃, the seventh zone is 170-250 ℃, the eighth zone is 170-240 ℃, the ninth zone is 155-230 ℃, the die head is 155-200 ℃, and the rotating speed is 50-250 rpm.
The parameters of the single screw extruder are as follows: the first area is 110-170 ℃, the second area is 170-240 ℃, the third area is 180-240 ℃, the fourth area is 165-200 ℃, and the rotating speed is 25-100 rpm.
The printing temperature of the outer wall of the 3D printing is 170-230 ℃, and the printing temperature of the filling layer is as follows: 225 to 245 ℃.
The model can adjust the overall dimension specification of the device through the design of the 3D printing structure according to the actual application condition, control the wall thickness and the volume of the model, and consider the density of resin, so that the overall density of the designed device is equivalent to the density of liquid, and the effect of self-suspending in the liquid is achieved.
The catalyst is selected from TiO2、ZnO、CdS、g-C3N4、Bi2O3、SnO2、ZrO2、ZnGa2O4Or a photocatalytic material based on the above-mentioned materials.
The heat treatment is a thermal deposition process.
The 3D printing photocatalytic device can be applied to photocatalytic degradation of pollutants and photocatalytic water splitting for hydrogen production and oxygen production.
The specific technical scheme is as follows: a preparation method of a 3D printing self-suspension photocatalytic device is characterized by comprising the following steps:
1) uniformly mixing ABS and modified resin according to the proportion of 70-85: 15-30 by a high-speed mixer, carrying out melt blending by a double-screw extruder, and carrying out extrusion granulation to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single screw extruder, cooling the extruded filament by water cooling, and drawing and controlling the wire diameter by a tractor to prepare a wire with the wire diameter of 1.75 +/-0.05 mm;
3) through model design, printing the outer wall of the model by the wire obtained in step 2), printing the inner filling of the model by the water-soluble PVA wire, and reserving 2-6 holes in the model, wherein the hole diameter is 0.2-0.6 cm;
4) dispersing 0.4-1.5 wt% of photocatalyst in isopropanol, placing the device obtained in step 3) and isopropanol according to the volume ratio of 1: 1-1: 10 after ultrasonic dispersion, naturally drying, and then placing in an oven to carry out heat treatment for 5-30 min at 130-170 ℃;
5) and (3) putting the device obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 hour, washing with the deionized water for 4-6 times to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60-80 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
The polymer for modifying the plastic substrate is selected from one or more of thermoplastic polyurethane elastomer rubber (TPU), thermoplastic elastomer (TPE), acrylonitrile-styrene copolymer (SAN), Polycarbonate (PC) and polyamide-6 (PA 6).
The parameters of the double-screw extruder are as follows: the first zone is 85-135 ℃, the second zone is 115-165 ℃, the third zone is 135-180 ℃, the fourth zone is 150-195 ℃, the fifth zone is 160-210 ℃, the sixth zone is 170-230 ℃, the seventh zone is 170-250 ℃, the eighth zone is 170-240 ℃, the ninth zone is 155-230 ℃, the die head is 155-200 ℃, and the rotating speed is 50-250 rpm.
The parameters of the single screw extruder are as follows: the first area is 110-170 ℃, the second area is 170-240 ℃, the third area is 180-240 ℃, the fourth area is 165-200 ℃, and the rotating speed is 25-100 rpm.
The printing temperature of the outer wall of the 3D printing is 170-240 ℃, and the printing temperature of the filling layer is as follows: 225 to 245 ℃.
The model can adjust the overall dimension specification of the device through the design of the 3D printing structure according to the actual application condition, control the wall thickness and the volume of the model, and consider the density of resin, so that the overall density of the designed device is equivalent to the density of liquid, and the effect of self-suspending in the liquid is achieved.
The catalyst may be any photocatalyst used, such as TiO2、ZnO、CdS、g-C3N4、Bi2O3、SnO2、ZrO2、ZnGa2O4Or photocatalytic materials based on these materials.
The heat treatment is a thermal deposition process.
The 3D printing photocatalytic device can be applied to photocatalytic degradation of pollutants and photocatalytic water splitting for hydrogen production and oxygen production.
The sheet obtained by any of the above-described production methods of the present invention. The loading capacity of the sheet catalyst can reach 10-40% of the amount of the added catalyst.
The invention has the beneficial effects that: the method is suitable for photocatalytic degradation of pollutants and photolysis of water to produce hydrogen and oxygen. The invention utilizes the glass transition temperature of the sheet material to ensure that the catalyst can be firmly loaded on the sheet material. The density of the sheet material can be adjusted to enable the sheet material to be suspended on the liquid surface, so that the catalyst can effectively utilize light, and the difficulties that the suspension liquid in a photocatalytic system has high turbidity, the photocatalyst is difficult to recover and recycle and the like are solved.
Drawings
Fig. 1 is a product diagram of a 3D printed self-suspended photocatalytic device with a hollow structure prepared in example 1 of the present invention.
Fig. 2 is a graph showing the change of hydrogen production by photolysis of water with a same mass catalyst in a 3D printed self-suspended photocatalytic device with a hollow structure prepared in example 1 of the present invention over time.
Fig. 3 is a time-dependent change curve of a 3D printed self-suspended photocatalytic device with a hollow structure and a homogeneous catalyst for photocatalytic degradation of tetracycline hydrochloride prepared in example 2 of the present invention.
Fig. 4 is a graph showing photolysis water cycle performance of a 3D printed self-suspended photocatalytic device having a hollow structure prepared in example 1 according to the present invention.
Fig. 5 is a graph showing the cycle performance of photocatalytic degradation of tetracycline hydrochloride with time by using a 3D printed self-suspending photocatalytic device having a hollow structure prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after 8 kg of ABS and 2 kg of TPU are mixed uniformly by a high-speed mixer, the mixture is melted and blended by a double-screw extruder, and the parameters of the double screws are as follows: extruding and granulating at the first area of 100 ℃, the second area of 125 ℃, the third area of 140 ℃, the fourth area of 155 ℃, the fifth area of 165 ℃, the sixth area of 185 ℃, the seventh area of 195 ℃, the eighth area of 180 ℃, the ninth area of 170 ℃, a die head of 165 ℃ at the rotating speed of 200 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 120 ℃, the second zone is 180 ℃, the third zone is 195 ℃, the fourth zone is 170 ℃, the rotating speed is 50 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and the wire diameter is controlled to be made into a wire rod with the wire diameter of 1.75 +/-0.05 mm;
3) designing a square sheet with the side length of 5 cm, the height of 0.2 cm and the wall thickness of 0.08 cm, printing the outer wall of the square sheet by the wire obtained in the step 2), wherein the printing temperature is 190 ℃, the interior of the model is filled with the water-soluble PVA wire for printing, the printing temperature is 230 ℃, and 2 holes with the aperture of 0.3 cm are reserved in the model;
4) 0.4 g of Pt-hemicellulose-TiO is taken2Dispersing in 100 mL of isopropanol, carrying out ultrasonic treatment for 30min, adding the square slices obtained in the step 3), naturally airing, and then placing into an oven to carry out heat treatment for 10 min at 150 ℃.
5) And (3) putting the square sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 h, washing for 5 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
6) A300W xenon lamp is used as a light source (placed in a double-layer glass jacket (communicated with condensed water), an optical filter ensures that the incident light wavelength is between 420 and 800 nm), a hollow 3D printed self-suspension photocatalytic square sheet is added into 100 mL of aqueous solution, a water photolysis experiment is carried out, the hydrogen yield per hour is detected by using a gas chromatograph for 5 hours in total, and a hydrogen production activity diagram of the hollow 3D printed self-suspension photocatalytic square sheet subjected to multiple water photolysis under the visible light condition is obtained, and specifically shown in fig. 2 and 4.
Example 2:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after 8.5 kg of ABS and 1.5 kg of TPU are mixed uniformly by a high-speed mixer, the mixture is melted and blended by a double-screw extruder, and the parameters of the double screws are as follows: extruding and granulating at the temperature of 110 ℃ in the first area, 130 ℃ in the second area, 155 ℃ in the third area, 170 ℃ in the fourth area, 185 ℃ in the fifth area, 195 ℃ in the sixth area, 200 ℃ in the seventh area, 190 ℃ in the eighth area, 175 ℃ in the ninth area and 165 ℃ in a die head at the rotating speed of 150 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 120 ℃, the second zone is 190 ℃, the third zone is 200 ℃, the fourth zone is 170 ℃, the rotating speed is 50 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and controlled in wire diameter to be made into wires with the wire diameter of 1.75 +/-0.05 mm;
3) designing a circular sheet with the radius of 2 cm, the height of 0.2 cm and the wall thickness of 0.08 cm, printing the outer wall of the circular sheet by the wire obtained in the step 2), wherein the printing temperature is 200 ℃, the inside of the model is filled with water-soluble PVA wires for printing, the printing temperature is 235 ℃, and 3 holes with the aperture of 0.4 cm are reserved in the model;
4) 0.8 g of TiO was taken2Dispersing in 100 mL of isopropanol, carrying out ultrasonic treatment for 30min, adding the round slices obtained in the step 3), naturally airing, and then placing into an oven to carry out heat treatment for 25 min at 140 ℃.
5) And (3) putting the round sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 h, washing for 4 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
6) A300W xenon lamp is used as a light source (placed in a double-layer glass jacket (condensed water is introduced), a simulated sunlight filter is used), a 3D printing self-suspension photocatalytic circular sheet with a hollow structure is added into 100 mL tetracycline hydrochloride aqueous solution with the concentration of 30 mg/L, a photocatalytic degradation experiment is carried out, 4 mL tetracycline hydrochloride aqueous solution is taken at intervals of 30min for ultraviolet-visible spectrum analysis (the concentration change of the tetracycline hydrochloride aqueous solution in the degradation process is determined according to the light absorption value at 357 nm of a sample), and the performance diagram of the 3D printing self-suspension photocatalytic circular sheet with the hollow structure for carrying out photocatalytic degradation on tetracycline hydrochloride for multiple times under the condition of visible light is obtained, and is specifically shown in fig. 3 and fig. 5.
Example 3:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after 7 kg of ABS and 3 kg of TPU are uniformly mixed by a high-speed mixer, the mixture is melted and blended by a double-screw extruder, and the parameters of the double screws are as follows: extruding and granulating at 90 ℃ in the first region, 120 ℃ in the second region, 145 ℃ in the third region, 160 ℃ in the fourth region, 170 ℃ in the fifth region, 180 ℃ in the sixth region, 185 ℃ in the seventh region, 175 ℃ in the eighth region, 165 ℃ in the ninth region and 160 ℃ in a die head at the rotating speed of 220 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 120 ℃, the second zone is 170 ℃, the third zone is 185 ℃, the fourth zone is 170 ℃, the rotating speed is 45 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and the wire diameter is controlled to be made into a wire rod with the wire diameter of 1.75 +/-0.05 mm;
3) designing a circular sheet with the radius of 8 cm, the height of 0.3 cm and the wall thickness of 0.08 cm, printing the outer wall of the circular sheet by the wire obtained in the step 2), wherein the printing temperature is 185 ℃, the inside of the model is filled with the wire printed by the water-soluble PVA, the printing temperature is 235 ℃, and 4 holes with the aperture of 0.5 cm are reserved in the model;
4) dispersing 0.6g of ZnO in 100 mL of isopropanol, performing ultrasonic treatment for 30min, adding the round slice obtained in the step 3), naturally drying, and then putting into an oven to perform heat treatment for 30min at 160 ℃.
5) And (3) putting the round sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 h, washing for 6 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 70 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
Example 4:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after 8 kg of ABS and 2 kg of TPU are mixed uniformly by a high-speed mixer, the mixture is melted and blended by a double-screw extruder, and the parameters of the double screws are as follows: extruding and granulating at the first area of 100 ℃, the second area of 125 ℃, the third area of 145 ℃, the fourth area of 155 ℃, the fifth area of 165 ℃, the sixth area of 186 ℃, the seventh area of 195 ℃, the eighth area of 180 ℃, the ninth area of 170 ℃, a die head of 165 ℃ at the rotating speed of 120 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 125 ℃, the second zone is 180 ℃, the third zone is 195 ℃, the fourth zone is 170 ℃, the rotating speed is 60 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and the wire diameter is controlled to be made into a wire rod with the wire diameter of 1.75 +/-0.05 mm;
3) designing an equilateral triangle sheet with the side length of 8 cm, the height of 0.24 cm and the wall thickness of 0.10 cm, printing the outer wall of the equilateral triangle sheet by the wire obtained in the step 2), wherein the printing temperature is 185 ℃, the printing temperature is 235 ℃, and 3 holes with the aperture of 0.4 cm are reserved in the model;
4) dispersing 1.0 g CdS in 100 mL isopropanol, performing ultrasonic treatment for 30min, adding the equilateral triangle slice obtained in the step 3), naturally drying, and placing in an oven for heat treatment at 130 ℃ for 10 min.
5) And (3) putting the equilateral triangle sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 hour, washing the equilateral triangle sheet for 5 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying the equilateral triangle sheet in an oven at 60 ℃, and melting the wire obtained in the step 2) and then sealing and blocking the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
Example 5:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after 8 kg of PLA and 2 kg of PC are uniformly mixed by a high-speed mixer, the mixture is melted and blended by a double-screw extruder, wherein the parameters of the double screws are as follows: extruding and granulating at 120 ℃ in the first area, 160 ℃ in the second area, 175 ℃ in the third area, 190 ℃ in the fourth area, 200 ℃ in the fifth area, 210 ℃ in the sixth area, 225 ℃ in the seventh area, 215 ℃ in the eighth area, 200 ℃ in the ninth area and 190 ℃ in a die head at the rotating speed of 80 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 160 ℃, the second zone is 225 ℃, the third zone is 220 ℃, the fourth zone is 190 ℃, the rotating speed is 60 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and the wire diameter is controlled to be made into a wire rod with the wire diameter of 1.75 +/-0.05 mm;
3) designing a rectangular sheet with the length of 10 cm, the width of 8 cm, the height of 0.3 cm and the wall thickness of 0.12 cm, printing the outer wall of the rectangular sheet by the wire obtained in the step 2), wherein the printing temperature is 215 ℃, the inside of the model is filled with water-soluble PVA wires for printing, the printing temperature is 240 ℃, and 3 holes with the aperture of 0.3 cm are reserved in the model;
4) take 0.4 g g-C3N4Dispersing in 100 mL of isopropanol, carrying out ultrasonic treatment for 30min, adding the rectangular sheet obtained in the step 3), naturally drying, and then placing in an oven to carry out heat treatment for 20 min at 160 ℃.
5) And (3) putting the rectangular sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 h, washing for 4 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
Example 6:
a preparation method of a 3D printing self-suspension photocatalytic device comprises the following steps:
1) after being uniformly mixed by a high-speed mixer, 7 kg of ABS and 3 kg of PA6 are melted and blended by a double-screw extruder, wherein the parameters of the double screws are as follows: extruding and granulating at 130 ℃ in the first area, 160 ℃ in the second area, 175 ℃ in the third area, 190 ℃ in the fourth area, 200 ℃ in the fifth area, 220 ℃ in the sixth area, 230 ℃ in the seventh area, 220 ℃ in the eighth area, 200 ℃ in the ninth area and 190 ℃ in a die head at the rotating speed of 150 rpm to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single-screw extruder, wherein the parameters of the single-screw extruder are as follows: the first zone is 150 ℃, the second zone is 220 ℃, the third zone is 230 ℃, the fourth zone is 190 ℃, the rotating speed is 50 rpm, the extruded filaments are cooled by water, and the drawn filaments are drawn by a drawing machine and the wire diameter is controlled to be made into a wire rod with the wire diameter of 1.75 +/-0.05 mm;
3) designing a rectangular sheet with the length of 10 cm, the width of 5 cm, the height of 0.15 cm and the wall thickness of 0.06 cm, printing the outer wall of the rectangular sheet by the wire obtained in the step 2), wherein the printing temperature is 220 ℃, the interior of the model is filled with water-soluble PVA wires for printing, the printing temperature is 240 ℃, and 4 holes with the aperture of 0.3 cm are reserved in the model;
4) 0.4 g of SnO2Dispersing in 100 mL of isopropanol, carrying out ultrasonic treatment for 30min, adding the rectangular sheet obtained in the step 3), naturally drying, and then placing in an oven to carry out heat treatment for 20 min at 165 ℃.
5) And (3) putting the rectangular sheet obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 h, washing for 6 times by using the deionized water to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A preparation method of a 3D printing self-suspension photocatalytic device is characterized by comprising the following steps:
1) uniformly mixing ABS and modified resin according to the proportion of 70-85: 15-30 by a high-speed mixer, carrying out melt blending by a double-screw extruder, and carrying out extrusion granulation to obtain wire master batches;
2) melting and extruding the wire master batch obtained in the step 1) through a single screw extruder, cooling the extruded filament by water, and drawing and controlling the wire diameter by a drawing machine to prepare a wire with the wire diameter of 1.75 +/-0.05 mm;
3) through model design, printing the outer wall of the model by the wire obtained in the step 2), printing the inner filling of the model by the water-soluble PVA wire, and reserving 2-6 holes in the model, wherein the hole diameter is 0.2-0.6 cm;
4) dispersing 0.4-1.5 wt% of photocatalyst in isopropanol, placing the device obtained in the step 3) and the isopropanol according to the volume ratio of less than 1: 1-1: 10 after ultrasonic dispersion, naturally airing, and placing in an oven for heat treatment at 130-170 ℃ for 5-30 min; the catalyst is selected from TiO2、ZnO、CdS、g-C3N4、Bi2O3、SnO2、ZrO2、ZnGa2O4Or a photocatalytic material based on the above-mentioned materials;
5) and (3) putting the device obtained in the step 4) into deionized water, performing ultrasonic treatment for 1 hour, washing with the deionized water for 4-6 times to remove the water-soluble PVA filling layer and the catalyst with the weak surface, drying in an oven at 60-80 ℃, melting the wire rod obtained in the step 2), and then sealing the hole to obtain the 3D printing self-suspension photocatalytic device with the hollow structure.
2. The preparation method of the 3D printing self-suspending photocatalytic device according to claim 1, wherein the modified resin is one or more selected from thermoplastic elastomer (TPE), acrylonitrile-styrene copolymer (SAN), Polycarbonate (PC), and polyamide-6 (PA 6).
3. The preparation method of the 3D printing self-suspending photocatalytic device according to claim 1, wherein the parameters of the twin-screw extruder are as follows: the first zone is 85-135 ℃, the second zone is 115-165 ℃, the third zone is 135-180 ℃, the fourth zone is 150-195 ℃, the fifth zone is 160-210 ℃, the sixth zone is 170-230 ℃, the seventh zone is 170-250 ℃, the eighth zone is 170-240 ℃, the ninth zone is 155-230 ℃, the die head is 155-200 ℃, and the rotating speed is 50-250 rpm.
4. The preparation method of the 3D printing self-suspending photocatalytic device according to claim 1, wherein the parameters of the single-screw extruder are as follows: the first area is 110-170 ℃, the second area is 170-240 ℃, the third area is 180-240 ℃, the fourth area is 165-200 ℃, and the rotating speed is 25-100 rpm.
5. The preparation method of the 3D printing self-suspending photocatalytic device according to claim 1, wherein the printing temperature of the outer wall of the 3D printing is 170-230 ℃, and the printing temperature of the filling layer is as follows: 225 to 245 ℃.
6. The method for preparing the 3D printing self-suspending photocatalytic device according to claim 1, wherein the model can adjust the overall dimension of the device through the design of the 3D printing structure according to the actual application situation, control the wall thickness and the volume of the model, and consider the resin density, so that the overall density of the designed device is equivalent to the density of liquid, and the effect of self-suspending in the liquid is achieved.
CN202010556394.4A 2020-06-18 2020-06-18 Preparation method of 3D printing self-suspension photocatalytic device Active CN111645224B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976734A (en) * 2018-06-16 2018-12-11 福建师范大学 A kind of PLA3D printing wire rod preparation method with photocatalysis effect
CN109748351A (en) * 2019-02-11 2019-05-14 福建师范大学 A kind of preparation method of 3D printing photocatalytic device
CN109878069A (en) * 2019-02-11 2019-06-14 福建师范大学 A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976734A (en) * 2018-06-16 2018-12-11 福建师范大学 A kind of PLA3D printing wire rod preparation method with photocatalysis effect
CN109748351A (en) * 2019-02-11 2019-05-14 福建师范大学 A kind of preparation method of 3D printing photocatalytic device
CN109878069A (en) * 2019-02-11 2019-06-14 福建师范大学 A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device

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