CN113831110A - 3D printing porous coral and preparation method thereof - Google Patents

3D printing porous coral and preparation method thereof Download PDF

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CN113831110A
CN113831110A CN202111102877.8A CN202111102877A CN113831110A CN 113831110 A CN113831110 A CN 113831110A CN 202111102877 A CN202111102877 A CN 202111102877A CN 113831110 A CN113831110 A CN 113831110A
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coral
parts
blank
clay
preparation
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CN113831110B (en
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黄爱宾
徐睿
刘彩凤
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Hangzhou Dianzi University
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Abstract

The invention discloses a 3D printing porous coral and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing clay according to the following materials in parts by weight: clay: 5-15 parts; calcium carbonate: 50-65 parts; mxene powder: 1-3 parts; glycolide: 1-2 parts; calcium sulfate: 0-8 parts of a solvent; hydroxyapatite: 5-10 parts; carboxymethyl chitosan: 1-2 parts; anthocyanins: 0-1 part; curcumin: 0-0.8 part; sodium percarbonate: 0-5 parts; deionized water: 8-20 parts; the materials are prepared into ceramic clay which is stirred and dispersed at a high speed to prepare slurry; printing the slurry into a femoral-shaped structural coral blank by using a 3D printer, and blowing and drying by compressed air; thirdly, soaking the coral blank in a mixed solution of ethanol and water of lactic acid; and fourthly, placing the treated coral blank into a microwave oven for heating and firing, naturally cooling and taking out to obtain the 3D printed porous coral. The 3D printed porous coral has the advantages of safety, no toxicity, high mechanical strength and the like.

Description

3D printing porous coral and preparation method thereof
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a 3D printing porous coral and a preparation method thereof.
Background
The coral is a shell secreted by coral, the chemical component is mainly CaCO3 (calcium carbonate) and exists in the form of microcrystal calcite aggregate, a certain amount of organic matters exist in the ingredients, the shape is mostly dendritic, longitudinal stripes are arranged on the coral, the cross section of each monomer coral is provided with concentric circles and radial stripes, the coral is always white and also has a small amount of blue and black, the coral not only looks like branches, but also is bright and beautiful in color, can be used as an ornament, and has high medicinal value. The main component of coral is calcium carbonate, which has a porous structure similar to human skeleton. The artificial bone requires coral to have a microporous structure, so that new bone tissue can grow into the artificial bone.
The 3D printing technique is an additive manufacturing technique, which is a technique for constructing an object by using an adhesive material such as powdered metal or plastic based on a digital model file and by printing layer by layer. However, to date, ceramic 3D printing employed by the prior art has been very expensive and difficult to use, which makes it difficult to popularize among individual users.
Chinese patent application No. CN201910934314.1 discloses a device and method for 3D printing coral reef, the method provides a printing device and uses sand powder to print coral reef.
Chinese patent application No. CN201910489232.0 discloses a surface bacteriostatic morphology method of an implant of a 3D printing substrate, which uses polylactic acid and hydroxyapatite to print out coral which can be used for implanting teeth.
Chinese patent application No. CN201910925055.6 provides a latticed concrete artificial coral reef and a preparation method and application thereof, and the method uses 3D printed concrete to prepare a three-dimensional latticed coral structure.
None of the above patents mention the post-treatment process of the fired coral, and the firing temperature is high and the preparation cost is expensive.
Disclosure of Invention
Aiming at the current situation, the invention discloses a 3D printing porous coral and a preparation method thereof. According to the invention, the porous coral is prepared by 3D printing of the inorganic material and the organic polymer composite material. The basic idea of the invention is to print out a coral blank by using an FDM type common clay 3D printer, etch and make holes on the blank under the action of organic weak acid, use a (household) microwave oven as a heating source, perform microwave polymerization while heating and making ceramics, generate a polymer in situ, and color-mix coral by using anthocyanin, curcumin and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of 3D printing porous coral comprises the following steps:
step one, preparing clay according to the following materials in parts by weight:
clay: 5-15 parts of
Calcium carbonate: 50-65 parts of
Mxene powder (Ti3C2Tx structure): 1-3 parts of
Glycolide: 1-2 parts of
Calcium sulfate: 0 to 8 portions of
Hydroxyapatite: 5-10 parts of
Carboxymethyl chitosan: 1-2 parts of
Anthocyanins: 0 to 1 portion of
Curcumin: 0 to 0.8 portion
Sodium percarbonate: 0 to 5 portions of
Deionized water: 8-20 parts;
the materials are prepared into ceramic clay which is stirred and dispersed at a high speed to prepare slurry;
printing the slurry into a femoral-shaped structure coral blank by using a 3D printer, and blowing and drying by compressed air;
soaking the coral blank in a mixed solution of ethanol and water of lactic acid to ensure that calcium carbonate, sodium percarbonate and acid in the raw materials fully react to generate holes and the integrity of the blank is maintained;
and step four, placing the treated coral blank into a microwave oven for heating and firing, naturally cooling and taking out to obtain the 3D printed porous coral. Preferably, the clay is predominantly a ceramic clay of the kaolinite family.
Preferably, the calcium carbonate is colloidal calcium carbonate having a particle size of 1-5 μm.
Preferably, the calcium sulfate is food grade calcium sulfate, 900-1500 mesh.
Preferably, the Hydroxyapatite (HAP) is porous type HAP, 200-.
Preferably, carboxymethyl chitosan, molecular weight 20-80X 104Degree of substitution>1.6。
Further, in the first step, the ceramic clay raw material is prepared according to the proportion and is stirred and dispersed at a high speed for 30-50 minutes by mechanical stirring at 1500-.
Further, in the second step, the coral blank is printed by using an FDM type common clay 3D printer, and the shape of the coral blank can be controlled by software according to requirements.
Further, step three, soaking the coral blank in a mixed solution of ethanol/water of lactic acid (50% V: 50% V ethanol and water each 50% by volume) for 20-50 minutes to form pores, thus forming a porous structure.
And step four, naturally airing the coral blank for 2-8 hours. Putting the mould shell on the mould shell and then putting the mould shell into a microwave oven for heating and firing. The firing is carried out for 10 to 15 minutes by adopting low fire (150W), then the firing is carried out for 25 to 40 minutes by adopting medium fire (500W), and finally the firing is carried out for 25 to 45 minutes by adopting high fire (800W). Naturally cooling and taking out. And preparing the 3D printing porous coral.
The invention also discloses a 3D printing porous coral prepared by the preparation method.
The microwave polymerization and the microwave firing pottery making process are completed together, and the in-situ generated polymer plays a role in dispersing and bonding. According to the invention, polyglycolide generated by microwave polymerization is used as a dispersing agent and an adhesive by adopting microwave in-situ polymerization, and Mxene (Ti3C2Tx structure) is used as a high-temperature absorbent, under the action of microwaves, the Mxene absorbs microwave energy and then heats structural components such as clay, calcium carbonate and the like, so that the ceramic forming temperature is reduced, the high-temperature calcination process is avoided, the cracking caused by overhigh temperature is also avoided, and the energy is saved. In the preparation process, anthocyanin and curcumin are used for toning, and the primary color of natural coral is simulated.
The 3D printed porous coral prepared by the invention has the advantages of controllable shape and color, safety, no toxicity, low processing temperature, high mechanical strength and the like, and can be used in the field of artificial bone repair.
Drawings
FIG. 1 is a view showing a microstructure of the coral prepared (showing that the coral has a porous structure in the preparation method).
FIG. 2 is a graph showing the results of cytotoxicity test for the preparation of porous coral.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The weight fractions of clay raw materials, calcium carbonate, Mxene powder (Ti3C2Tx structure), glycolide, hydroxyapatite, carboxymethyl chitosan, anthocyanin, sodium percarbonate and deionized water are respectively as follows:
clay: 5 portions of
Calcium carbonate: 60 portions of
Mxene powder (Ti3C2Tx structure): 2 portions of
Glycolide: 2 portions of
Hydroxyapatite: 8 portions of
Carboxymethyl chitosan: 1 part of
Anthocyanins: 0.5 portion
Sodium percarbonate: 2 portions of
Deionized water: 20 portions of
After the raw materials are prepared, the raw materials are mechanically stirred at a high speed of 2000 r/min and dispersed for 30 min to prepare slurry. And printing the coral blank body into a femur-shaped structure by using a 3D printer, and blowing and drying by using compressed air. Soaking the coral blank in the mixed solution of ascorbic acid and ethanol/water (50%) for 50 min to make calcium carbonate, sodium percarbonate and acid in the raw materials fully react to generate pores and maintain the integrity of the blank. And (3) placing the treated blank into a microwave oven, firing for 15 minutes by using low fire (150W), continuing firing for 30 minutes by using medium fire (500W), and finally firing for 40 minutes by using high fire (800W). Naturally cooling and taking out. And preparing the 3D printing porous coral.
The microstructure of the porous coral prepared by the example of the present invention is shown in FIG. 1.
Example 2
The weight fractions of clay raw materials, calcium carbonate, Mxene powder (Ti3C2Tx structure), glycolide, calcium sulfate, hydroxyapatite, carboxymethyl chitosan, curcumin and deionized water are respectively as follows:
clay: 10 portions of
Calcium carbonate: 55 portions of
Mxene powder (Ti3C2Tx structure): 1.5 parts of
Glycolide: 1 part of
Calcium sulfate: 8 portions of
Hydroxyapatite: 5 portions of
Carboxymethyl chitosan: 1 part of
Curcumin: 0.5 portion
Deionized water: 10 portions of
The raw materials are stirred and dispersed for 40 minutes at a high speed by mechanical stirring at 1600 revolutions per minute after being prepared, and slurry is prepared. And printing the blank into a skull-shaped structure coral blank by using a 3D printer, and blowing and drying by using compressed air. Soaking the coral blank in the mixed solution of lactic acid and ethanol/water (50%) for 25 min to make the calcium carbonate in the raw material fully react with lactic acid to produce holes and maintain the integrity of the blank. And (3) placing the treated blank into a microwave oven, firing for 12 minutes by using low fire (150W), continuing firing for 25 minutes by using medium fire (500W), and finally firing for 35 minutes by using high fire (800W). Naturally cooling and taking out. And preparing the 3D printing porous coral.
According to the invention, a 3D printing technology, a microwave polymerization technology and a ceramic preparation technology are fused to prepare the 3D printing porous coral. The porous coral printed by 3D printing has the advantages of controllable shape and color, safety, no toxicity, low processing temperature, high mechanical strength and the like. The 3D printed porous coral can be used in the fields of artificial bone repair and the like.
The coral tree blank is prepared by adopting clay, calcium carbonate and hydroxyapatite as main materials for preparing a coral blank, Mxene powder (Ti3C2Tx structure) as a high-temperature absorption material, glycolide and carboxymethyl chitosan as dispersing agents, sodium percarbonate as a pore-forming agent, anthocyanin or curcumin as a toner, deionized water as a dispersing agent and a viscosity regulator, stirring at a high speed for dispersion to prepare ceramic slurry, and printing the coral tree by using a 3D (three-dimensional) pottery clay printer. Soaking the blank body in an ethanol/water mixed solution of ascorbic acid/lactic acid to prepare holes, and finally heating the blank body by a microwave oven to fire the holes to prepare the 3D printed porous coral.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A preparation method of 3D printing porous coral is characterized by comprising the following steps:
step one, preparing clay according to the following materials in parts by weight:
clay: 5-15 parts of
Calcium carbonate: 50-65 parts of
Mxene powder: 1-3 parts of
Glycolide: 1-2 parts of
Calcium sulfate: 0 to 8 portions of
Hydroxyapatite: 5-10 parts of
Carboxymethyl chitosan: 1-2 parts of
Anthocyanins: 0 to 1 portion of
Curcumin: 0 to 0.8 portion
Sodium percarbonate: 0 to 5 portions of
Deionized water: 8-20 parts;
the materials are prepared into ceramic clay which is stirred and dispersed at a high speed to prepare slurry;
printing the slurry into a femoral-shaped structure coral blank by using a 3D printer, and blowing and drying by compressed air;
step three, soaking the coral blank in a mixed solution of ethanol and water of lactic acid;
and step four, placing the treated coral blank into a microwave oven for heating and firing, naturally cooling and taking out to obtain the 3D printed porous coral.
2. The preparation method of the 3D printed porous coral according to claim 1, wherein in the step one, the clay is mechanically stirred at a high speed of 1500-.
3. The preparation method of the 3D printing porous coral according to claim 1, wherein in step three, the coral green body is soaked in an ethanol/water mixed solution of ascorbic acid/lactic acid for 20-50 minutes to form pores, thereby forming a porous structure.
4. The preparation method of the 3D printed porous coral, as claimed in claim 1, wherein in step four, the treated coral blank is naturally dried, put in after being covered with a mold shell, and fired with low fire for 10-15 minutes, then with medium fire for 25-40 minutes, and finally with high fire for 25-45 minutes.
5. The method of preparing a 3D printed porous coral according to any one of claims 1 to 4 wherein the clay is a ceramic clay of the kaolinite family.
6. The method of preparing a 3D printed porous coral according to any one of claims 1 to 4 wherein the calcium carbonate is colloidal calcium carbonate having a particle size of 1 to 5 μm.
7. The preparation method of 3D printed porous coral according to any one of claims 1 to 4, wherein the calcium sulfate is food grade calcium sulfate of 900-1500 mesh.
8. The method for preparing 3D printed porous coral according to any one of claims 1 to 4 wherein the hydroxyapatite is porous HAP with a pore size of 200-300 μm.
9. The method of preparing a 3D printed porous coral as claimed in any one of claims 1 to 4 wherein the carboxymethyl chitosan has a molecular weight of 20 to 80 x 104Degree of substitution>1.6。
10. A 3D printed porous coral prepared by the method of any one of claims 1 to 9.
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Citations (4)

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CN102643411A (en) * 2012-04-27 2012-08-22 孝感市易生新材料有限公司 Method for synthesizing polyglycolide and polylactic acid-glycolide copolymer by microwave irradiation
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