CN110698571A - Method for chemically treating crab shell powder, reinforced polylactic acid 3D printing material and preparation method thereof - Google Patents
Method for chemically treating crab shell powder, reinforced polylactic acid 3D printing material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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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
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- 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
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to the technical field of solid waste treatment and fused deposition modeling 3D printing, and particularly relates to a method for chemically treating crab shell powder. According to the invention, the waste crab shells are subjected to chemical treatment, so that the polylactic acid 3D printing material is prepared, the preparation process is simple, the added value of the crabs is improved, the environmental pollution is reduced, and the prepared polylactic acid 3D printing material not only has good mechanical property and printing property, but also is green, environment-friendly and unique in color.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment and fused deposition modeling 3D printing, and particularly relates to a method for chemically treating crab shell powder, a reinforced polylactic acid 3D printing material and a preparation method thereof.
Background
In recent years, with the annual increase of crab yield in China, how to effectively utilize waste crab shells generated in the processing process of the crabs reduces environmental pollution and improve the added value of products has important significance for the development of crab industry. The crab shell is rich in effective components such as chitin, protein, pigment, inorganic salt and the like, and how to effectively extract and reasonably utilize the effective components is always a research focus of people, and especially the extraction of chitin from waste crab shells draws extensive attention. At present, the method for extracting chitin from waste crab shells by adopting an acid-base method is a main effective utilization method. For example, chinese patent CN107629146A provides a method for extracting acid-soluble chitin from shrimp and crab shells, which uses an acid-base method to repeatedly treat shrimp and crab shells to prepare chitin, and the preparation process is simple, but requires a bleaching process with a sodium sulfite solution and the utilization rate of the crab shells is low. Chinese patent CN106478996A discloses a method for preparing calcium carbonate/chitin composite powder by using crab shells as raw materials and application thereof, wherein the method comprises the steps of removing protein and fat in crab shell powder by using alkaline solution, and then decoloring by using an oxidizing agent to obtain the composite powder. However, the process has low utilization rate of the waste crab shells and serious pollution, and particularly, the intermediate products generated in the chitin preparation process cannot be fully and effectively utilized.
In recent years, the preparation of 3D printing materials by compounding chitin as a reinforcing material with a polymer matrix has also become a hotspot for research and application. Chinese patent CN103319739A discloses a preparation method of a chitin nanofiber/polylactic acid composite membrane and a preparation method thereof, which effectively improve the toughness, mechanical properties and thermal stability of polylactic acid, but the process is complex and the preparation period is long. Chinese patent CN109337310A provides a degradable 3D printing composite material and a preparation method thereof, the degradable 3D printing material is obtained by compounding chitin, plant powder, salmon spine bone powder, silk fibroin and the like with Polycaprolactone (PCL), but the production process is difficult to control due to the complex raw material sources.
Polylactic acid as a completely biodegradable high molecular polymer has good physical and mechanical properties and processability, can meet the requirements of sustainable development, and is one of the most promising biodegradable high molecular materials at present. However, polylactic acid is poor in toughness and thermal stability and high in price, and thus the application field thereof is limited.
Disclosure of Invention
In order to recycle the waste crab shells more efficiently, reduce the pollution to the environment and simultaneously solve the defects of poor mechanical property, single color and the like of polylactic acid 3D printing materials, the invention mainly aims to provide a method for chemically treating crab shell powder. The method is realized by the following technical scheme:
a method for chemically treating crab shell powder is designed, and comprises the following steps:
(1) cleaning the surface of crab shell, crushing and sieving to obtain brown crab shell powder;
(2) soaking the obtained brown crab shell powder in a container containing a dilute acid solution, wherein the mass volume ratio of the crab shell powder to the dilute acid is 1: (5-15) g/mL, and the soaking time is 5-12 h; filtering, washing (until the washing liquid is neutral), and drying (at 80-100 deg.C) for 12-24h to obtain orange crab shell powder;
(3) adding the obtained orange crab shell powder into a container filled with an alkali solution, wherein the mass volume ratio of the crab shell powder to the alkali solution is 1: (3-15) g/mL, and stirring for 15-24h at 20-30 ℃; filtering, washing (until the washing liquid is neutral), and drying (at 80-100 deg.C) for 12-24h to obtain light red crab shell powder;
(4) repeatedly treating the obtained light red crab shell powder for 1 time through the step (2) and the step (3) in sequence to obtain light yellow crab shell powder;
(5) adding the obtained light red crab shell powder or light yellow crab shell powder into a container containing absolute ethyl alcohol, wherein the mass volume ratio of the crab shell powder to the absolute ethyl alcohol is 1: (4-10) g/mL, and stirring for 4-8h at 20-30 ℃; filtering, washing, and oven drying at 60-80 deg.C for 12-24 hr to obtain milky crab shell powder.
Preferably, the crab shells in the step (1) are one or two of portunids, blue crabs and hairy crabs; the mesh number of the crab shell powder in the step (1) is 50-300 meshes, and more preferably 200-300 meshes.
Preferably, the diluted acid solution in the step (2) is a solution of at least one of hydrochloric acid, phosphoric acid and acetic acid, and the concentration is 2-6 wt%.
Preferably, the alkali solution in step (3) is a solution of at least one of sodium hydroxide, potassium hydroxide and barium hydroxide, and the concentration is 3-8 wt%.
The invention also aims to provide a chemical treatment crab shell powder reinforced polylactic acid 3D printing material, which utilizes different structures and properties of the obtained crab shell powder with different colors to adjust the mechanical property and color of the polylactic acid 3D printing material so as to adapt to different application fields. The method is realized by the following technical scheme:
a chemically-treated crab shell powder reinforced polylactic acid 3D printing material is a blend containing chemically-treated crab shell powder, polylactic acid, a toughening agent and a lubricant; the chemically treated crab shell powder is at least one of the orange crab shell powder, light red crab shell powder, light yellow crab shell powder and milky white crab shell powder.
Preferably, the feed comprises the following raw materials in percentage by weight: 1-10% of chemically treated crab shell powder, 85-93% of polylactic acid, 1-5% of toughening agent and 1-5% of lubricant.
Preferably, the polylactic acid has a molecular weight of 1 × 105-5×106。
Preferably, the toughening agent is at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), and thermoplastic polyurethane elastomer (TPU).
Preferably, the lubricant is one or more of zinc stearate, calcium stearate and butyl stearate.
The preparation method of the chemically-treated crab shell powder reinforced polylactic acid 3D printing material comprises the following steps:
(1) uniformly mixing the chemically processed crab shell powder with polylactic acid, a toughening agent and a lubricant according to a certain proportion, and drying at 80-100 ℃ for 5-15h to obtain a blend for later use;
(2) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80-90 ℃ for 5-10 h for later use; wherein the temperatures of the sections 1-6 of the extruder are respectively 145-155 ℃, 150-160 ℃, 170-175 ℃, 175-180 ℃, 180-185 ℃ and 170-180 ℃, and the rotation speeds of the host and the feeder are respectively 15-30rpm and 5-15 rpm;
(3) drawing the obtained granules into 3D printing wires by a single screw extruder, wherein the temperatures of 1-4 sections of the extruder are respectively 160-;
(4) the rolled wire is printed by a desktop FDM type 3D printer, the temperature of a printing nozzle is 180-200 ℃, the diameter of the nozzle is 0.4mm, the printing speed is 30-80mm/min, and the temperature of a printing platform is 30-70 ℃.
Compared with the prior art, the invention has the following advantages and effects:
(1) according to the invention, through chemical treatment of the waste crab shells, brown crab shell powder, orange crab shell powder, light red crab shell powder, light yellow crab shell powder and milky crab shell powder can be respectively obtained, the obtained crab shell powder with different colors has different structures and performances, the added value of the crab product is improved, and the purposes of efficiently recycling the waste crab shells and slowing down the environmental pollution are realized.
(2) The crab shell powder reinforced polylactic acid 3D printing wire rod has natural color and luster, is green and environment-friendly, and has excellent mechanical property and better printing property; and the mechanical property and color of the polylactic acid 3D printing material can be adjusted by changing the chemical treatment method of the crab shell powder so as to adapt to different application fields.
Drawings
FIG. 1 is a scanning electron microscope image of light red crab shell powder in example 2;
FIG. 2 is a scanning electron microscope image of light yellow crab shell powder in example 3;
fig. 3 is a photograph of an orange crab shell treated in example 1 and a reinforced polylactic acid 3D printed wire prepared therefrom;
FIG. 4 is a photograph of a light red crab shell treated in example 2 and an enhanced polylactic acid 3D printed wire prepared therefrom;
FIG. 5 is a photograph of a yellowish crab shell treated in example 3 and a reinforced polylactic acid 3D printed wire prepared therefrom;
FIG. 6 is a photograph of milky white crab shells treated in example 4 and reinforced polylactic acid 3D printed wires prepared therefrom;
FIG. 7 is a photograph of milky white crab shells treated in example 5 and reinforced polylactic acid 3D printed wires prepared therefrom;
fig. 8 is a photograph of chemically untreated brown crab shells and their prepared reinforced polylactic acid 3D printed wires.
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.
The reagents used in the examples of the present invention are conventional raw materials or reagents unless otherwise specified, and the experimental methods used are conventional in the art unless otherwise specified. The specific method for testing the mechanical property of the composite material is as follows: the tensile test is executed according to the national standard GB/T1040-; the bending test is carried out according to the national standard GB/T9341-2008, and the bending speed is 5 mm/min.
Example 1
A preparation method of a polylactic acid 3D printing composite material with an orange-red appearance enhancement comprises the following steps:
(1) washing the abandoned swimming crab shells with water, and removing mud and other impurities on the crab shells; then crushing and sieving the crab shell powder by a high-speed crusher to obtain 250-mesh brown crab shell powder;
(2) soaking the crab shell powder obtained in the step (1) in a container containing 4% hydrochloric acid, wherein the mass volume ratio of the crab shell powder to the hydrochloric acid is 1: 10, soaking for 10 hours, then filtering, washing to be neutral, and drying for 20 hours at 100 ℃ to obtain orange crab shell powder;
(3) mixing 5% of the orange crab shell powder obtained in the step (2), 90% of polylactic acid, 2% of SEBS and 3% of lubricant zinc stearate through a high-speed mixer to obtain a mixture, and drying the mixture for 5 hours at 85 ℃ for later use;
(4) and melting and extruding the obtained mixture by a double-screw extruder, granulating to obtain granules, and fully drying at 80 ℃ for 16 hours for later use. Wherein the temperatures of 1-6 sections of the extruder are 145 ℃, 155 ℃, 170 ℃, 175 ℃, 180 ℃ and 175 ℃, and the rotating speeds of the host machine and the feeder are 20rpm and 10 rpm respectively;
(5) drawing the obtained granules into 3D printing wires by a single-screw extruder, wherein the temperatures of 1-4 sections of the extruder are 165 ℃, 175 ℃, 180 ℃, 170 ℃ and the traction speed is 30 mm/s respectively, so that the wires are obtained, the diameter of the obtained wires is about 1.75mm, and the diameter error is within +/-0.05, which is shown in figure 3;
(6) the rolled wire rods are printed through a desktop FDM type 3D printer, the temperature of a printing spray head is 200 ℃, the diameter of a nozzle is 0.4mm, the printing speed is 40mm/min, and the temperature of a printing platform is 45 ℃.
For comparison, the whole crab shell is treated by the method of the embodiment, and the appearance is shown in figure 3. And (3) performing mechanical property test on the polylactic acid 3D printing material standard sample strip prepared by 3D printing according to the national standard, wherein the test results of the mechanical property and the 3D printing property are shown in Table 1.
Example 2
A preparation method of polylactic acid 3D printing composite material with light red appearance enhancement comprises the following steps:
(1) washing the crab shell of the abandoned portunid by water, removing mud and other impurities on the crab shell, and then obtaining 300-mesh brown crab shell powder by high-speed crushing and sieving;
(2) soaking the crab shell powder obtained in the step (1) in a container containing 6% phosphoric acid, wherein the mass volume ratio of the crab shell powder to dilute acid is 1: 8, soaking for 12h, filtering, washing to be neutral, and drying at 100 ℃ for 20h to obtain orange crab shell powder;
(3) adding the orange crab shell powder obtained in the step (2) into a container filled with 6% potassium hydroxide solution, wherein the mass volume ratio of the crab shell powder to the alkali solution is 1: 5, stirring for 20 hours at 30 ℃, filtering, washing to be neutral, drying for 12 hours at 100 ℃ to obtain light red crab shell powder, and performing a scanning electron microscope (see figure 1), wherein the crab shell powder is not in a complete filling state but partially hollow, which is helpful for improving the contact area between the crab shell powder and the matrix polylactic acid, so that the mechanical property is improved;
(4) mixing 8% of the light red crab shell powder obtained in the step (3), 86% of polylactic acid, 4% of SBS and 2% of lubricant calcium stearate through a high-speed mixer to obtain a mixture, and drying the mixture for 10 hours at 85 ℃ for later use; the remaining experimental procedures were the same as in steps (4), (5) and (6) of example 1.
The appearance of the crab shell treated by the same method and the polylactic acid 3D printing wire are shown in figure 4, and the mechanical property and 3D printing property test results are shown in table 1.
Example 3
A preparation method of a polylactic acid 3D printing composite material with a faint yellow appearance enhancement comprises the following steps:
(1) washing the crab shell of the abandoned portunid by water, removing mud and other impurities on the crab shell, and then obtaining brown crab shell powder with 200 meshes by high-speed crushing and sieving;
(2) soaking the crab shell powder obtained in the step (1) in a container containing 6% acetic acid, wherein the mass volume ratio of the crab shell powder to dilute acid is 1: 10, soaking for 10 hours, then filtering, washing to be neutral, and drying for 20 hours at 100 ℃ to obtain orange crab shell powder; by scanning an electron microscope, as shown in fig. 2, the crab shell powder has a more obvious hollow structure, and the contact area between the crab shell powder and the matrix polylactic acid is larger, so that the mechanical property of the material is further improved;
(3) adding the orange crab shell powder obtained in the step (2) into a container filled with 6% sodium hydroxide solution, wherein the mass volume ratio of the crab shell powder to the alkali solution is 1: stirring for 20h at the temperature of 8 and 25 ℃, then filtering, washing to be neutral, and drying for 15h at the temperature of 100 ℃ to obtain light red crab shell powder;
(4) repeatedly treating the light red crab shell powder obtained in the step (3) for 1 time through the step (2) and the step (3) to obtain light yellow crab shell powder;
(5) mixing 5% of the light yellow crab shell powder obtained in the step (4), 87% of polylactic acid, 3% of SEBS (styrene-ethylene-butylene-styrene copolymer) and 5% of lubricant calcium stearate by using a high-speed mixer to obtain a mixture, and drying the mixture for 12 hours at 80 ℃ for later use;
the remaining experimental procedures were the same as in steps (4), (5) and (6) of example 1. The appearance diagram and the polylactic acid 3D printing wire of the crab shell prepared by the same method in the embodiment are shown in figure 5, and the mechanical property and the 3D printing property test result are shown in table 1.
Example 4
A preparation method of a polylactic acid 3D printing composite material with milky appearance enhancement comprises the following steps:
(1) washing the crab shell of the abandoned portunid by water, removing mud and other impurities on the crab shell, and then crushing and sieving at high speed to obtain crab shell powder of 150 meshes;
(2) soaking the crab shell powder obtained in the step (1) in a container filled with 4% acetic acid, wherein the mass volume ratio of the crab shell powder to dilute acid is 1: 8, soaking for 12h, filtering, washing to be neutral, and drying at 100 ℃ for 20h to obtain orange crab shell powder;
(3) adding the orange crab shell powder obtained in the step (2) into a container filled with 5% sodium hydroxide solution, wherein the mass volume ratio of the crab shell powder to the alkali solution is 1: stirring at 30 deg.C for 18 h, filtering, washing to neutrality, and oven drying at 80 deg.C for 15h to obtain light red crab shell powder;
(4) putting the light red crab shell powder obtained in the step (3) into a container filled with absolute ethyl alcohol, wherein the mass volume ratio of the crab shell powder to the absolute ethyl alcohol is 1: stirring for 5h at 25 ℃, then filtering, washing, and drying for 20h at 100 ℃ to obtain milky crab shell powder;
(5) mixing 10% of the milky crab shell powder obtained in the step (4), 84% of polylactic acid, 3% of TPU and 3% of lubricant calcium stearate through a high-speed mixer to obtain a mixture, and drying the mixture for 6 hours at 85 ℃ for later use;
the remaining experimental procedures were the same as in steps (4), (5) and (6) of example 1. The appearance of the crab shell and the polylactic acid 3D printing wire prepared by the same method in this example is shown in fig. 6, and the mechanical property and 3D printing property test results are shown in table 1.
Example 5
A preparation method of a polylactic acid 3D printing composite material with milky appearance enhancement comprises the following steps:
(1) washing the crab shell of the abandoned portunid by water, removing mud and other impurities on the crab shell, and then crushing and sieving at high speed to obtain crab shell powder of 200 meshes;
(2) soaking the crab shell powder obtained in the step (1) in a container filled with 4% acetic acid, wherein the mass volume ratio of the crab shell powder to dilute acid is 1: 10, soaking for 10 hours, then filtering, washing to be neutral, and drying for 24 hours at the temperature of 80 ℃ to obtain orange crab shell powder;
(3) adding the orange crab shell powder obtained in the step (2) into a container filled with 4% sodium hydroxide solution, wherein the mass volume ratio of the crab shell powder to the alkali solution is 1: stirring for 24h at 25 ℃, filtering, washing to be neutral, and drying for 15h at 80 ℃ to obtain light red crab shell powder;
(4) repeatedly treating the light red crab shell powder obtained in the step (3) for 1 time through the step (2) and the step (3) to obtain light yellow crab shell powder;
(5) putting the light yellow shell powder obtained in the step (4) into a container filled with absolute ethyl alcohol, wherein the mass volume ratio of the crab shell powder to the absolute ethyl alcohol is 1: stirring for 6h at the temperature of 8 and 25 ℃, then filtering, washing, and drying for 20h at the temperature of 80 ℃ to obtain milky crab shell powder;
(6) mixing 10% of the milky crab shell powder obtained in the step (4), 84% of polylactic acid, 3% of TPU and 3% of lubricant calcium stearate through a high-speed mixer to obtain a mixture, and drying the mixture for 6 hours at 85 ℃ for later use;
the remaining experimental procedures were the same as in steps (4), (5) and (6) of example 1. The appearances of the crab shells and the polylactic acid 3D printing wire prepared by the same method in this embodiment are shown in fig. 7, the mechanical properties and the 3D printing properties of the composite material are further improved, and the specific test results are shown in table 1.
Comparative example 1
A preparation method of a polylactic acid 3D printing composite material with a brown appearance and enhanced by waste crab shell powder without chemical treatment comprises the following steps:
(1) washing the crab shell of the abandoned portunid by water, removing mud and other impurities on the crab shell, and then obtaining brown crab shell powder with 200 meshes by high-speed crushing and sieving;
(2) mixing 5% of the brown crab shell powder prepared in the step (1), 90% of polylactic acid, 2% of SEBS and 3% of lubricant zinc stearate through a high-speed mixer to obtain a blend, and drying for 5 hours at 90 ℃ for later use;
the remaining experimental procedures were the same as in steps (4), (5) and (6) of example 1. The appearance and polylactic acid 3D printing wire of the crab shell prepared by the same method of the comparative example are shown in figure 8, and the mechanical property and 3D printing property test results are shown in table 1.
Comparative example 2
A preparation method of a polylactic acid 3D printing material without adding crab shell powder comprises the following steps:
(1) mixing 95% of polylactic acid, 2% of SEBS and 3% of lubricant zinc stearate by a high-speed mixer to obtain a blend, and drying for 5 hours at 85 ℃ for later use;
the remaining experimental procedures were the same as those of the procedures (4), (5) and (6) in example 1. The mechanical properties and the 3D printed material performance test results of the pure polylactic acid 3D printed material prepared by the comparative example are shown in Table 1.
The detection result shows that the chemically-treated crab shell powder reinforced polylactic acid 3D printing composite material prepared by the invention has excellent mechanical property, natural color and environmental protection, meets the mechanical strength and appearance requirements of polylactic acid 3D printing materials required in the market, and meets the technical requirements of FDM type 3D printing.
TABLE 1 appearance and Properties of chemically treated crab shells, enhanced polylactic acid 3D printed materials
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Other variations will be anticipated by those skilled in the art in view of the description of the invention, and such variations are intended to be included within the scope of the invention.
Claims (13)
1. A method for chemically treating crab shell powder is characterized by comprising the following steps:
(1) cleaning the surface of crab shell, crushing and sieving to obtain brown crab shell powder;
(2) and soaking the obtained brown crab shell powder in a container containing a dilute acid solution, filtering, washing and drying to obtain the orange crab shell powder.
2. A method of chemically treating crab shell powder according to claim 1, wherein: the crab shell in the step (1) is one or two of portunid, blue crab and hairy crab; the mesh number of the crab shell powder in the step (1) is 50-300 meshes.
3. A method of chemically treating crab shell powder according to claim 1, wherein: the dilute acid solution in the step (2) is at least one solution of hydrochloric acid, phosphoric acid and acetic acid, and the concentration is 2-6 wt%; the mass volume ratio of the brown crab shell powder to the dilute acid in the step (2) is 1: (5-15) g/mL, and the soaking time is 5-12 h.
4. The method of chemically treating crab shell powder according to claim 1, further comprising the step (3): adding the obtained orange crab shell powder into a container filled with an alkali solution, uniformly stirring, filtering, washing, and then drying to obtain light red crab shell powder.
5. A method for chemically treating crab shell powder according to claim 4, wherein the alkali solution of step (3) is a solution of at least one of sodium hydroxide, potassium hydroxide and barium hydroxide, at a concentration of 3-8 wt%; the mass volume ratio of the orange crab shell powder to the alkali solution used in the step (3) is 1: (3-15) g/mL, and stirring at 20-30 ℃ for 15-24 h.
6. A method for chemically treating crab shell powder according to claim 4, further comprising the step (4): and (3) repeatedly treating the obtained light red crab shell powder for 1 time through the step (2) and the step (3) in sequence to obtain light yellow crab shell powder.
7. A method of chemically treating crab shell powder according to claim 6, further comprising the step (5): adding the obtained light red crab shell powder or light yellow crab shell powder into a container containing absolute ethyl alcohol, uniformly stirring, filtering, washing, and then drying to obtain milky crab shell powder.
8. A method of chemically treating crab shell powder according to claim 7, wherein: the mass volume ratio of the crab shell powder to the absolute ethyl alcohol in the step (5) is 1: (4-10) g/mL, and stirring at 20-30 ℃ for 4-8 h.
9. A chemically treated crab shell powder reinforced polylactic acid 3D printing material, which is a blend comprising the chemically treated crab shell powder obtained in any one of claims 1 to 8, and polylactic acid, a toughening agent and a lubricant.
10. The reinforced polylactic acid 3D printing material according to claim 9, wherein: comprises the following raw materials in percentage by weight: 1-10% of chemically treated crab shell powder, 85-93% of polylactic acid, 1-5% of toughening agent and 1-5% of lubricant.
11. The reinforced polylactic acid 3D printing material according to claim 9, wherein: the molecular weight of the polylactic acid is 1 multiplied by 105-5×106(ii) a The toughening agent is at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS) and thermoplastic polyurethane elastomer (TPU); the lubricant is one or more of zinc stearate, calcium stearate and butyl stearate.
12. The preparation method of the reinforced polylactic acid 3D printing material as claimed in any one of claims 9 to 11, which is characterized by comprising the following steps:
(1) uniformly mixing the chemically processed crab shell powder with polylactic acid, a toughening agent and a lubricant according to a certain proportion, and drying at 80-100 ℃ for 5-15h to obtain a blend for later use;
(2) melting and extruding the obtained blend by a double-screw extruder, granulating to obtain granules, and fully drying at 80-90 ℃ for 5-10 h for later use;
(3) and (3) drawing the obtained granules into a 3D printing wire rod through a single-screw extruder to obtain the printing wire rod.
13. The method of manufacturing according to claim 12, wherein: the temperatures of the sections 1-6 of the double-screw extruder are respectively 155 ℃ at 145-; the temperatures of the 1-4 sections of the single-screw extruder are respectively 160-170 ℃, 175-180 ℃ and 170-175 ℃, and the traction speed is 30-40 mm/s.
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