CN117800655A - High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method - Google Patents
High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method Download PDFInfo
- Publication number
- CN117800655A CN117800655A CN202410022244.3A CN202410022244A CN117800655A CN 117800655 A CN117800655 A CN 117800655A CN 202410022244 A CN202410022244 A CN 202410022244A CN 117800655 A CN117800655 A CN 117800655A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- hydroxyapatite
- printing
- potassium
- precision
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 84
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 80
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 78
- 238000007639 printing Methods 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000011282 treatment Methods 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 239000000725 suspension Substances 0.000 description 11
- 239000000499 gel Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
-
- 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
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to the field of material science engineering, and discloses a high-precision 3D printing forming method of a hydroxyapatite/chitosan composite bracket with an interconnected porous structure by a room temperature one-step method. The method takes potassium-doped hydroxyapatite and chitosan as raw materials and comprises the following steps: preparing potassium-doped hydroxyapatite slurry; mixing potassium-doped hydroxyapatite slurry with chitosan solution; and extruding the 3D printing and forming at room temperature to obtain the one-step formed 3D printing interconnection porous structure composite material. The hydroxyapatite powder is prepared by potassium doping modification, does not need to be printed in a curing solution, does not need to be subjected to crosslinking treatment such as spraying curing solution and the like, and avoids the processes such as high-temperature treatment, sintering and the like. The 3D printing interconnection porous structure of the interconnection porous structure composite material is prepared, has a high-precision structure and excellent mechanical properties, and realizes normal-temperature one-step extrusion 3D printing molding. The 3D printing forming porous material prepared by the method has potential application value in the fields of water treatment, biomedical stents and the like.
Description
Technical Field
The invention belongs to the field of material science engineering, relates to a high-precision interconnected porous hydroxyapatite/chitosan composite material and a room-temperature one-step 3D printing forming method, and has certain application value in the fields of water treatment, biomedical stents and the like.
Background
Hydroxyapatite is widely recognized as an excellent scaffold material, however, conventional preparation methods, such as a foaming method, a sintering microsphere method, and a sol-gel method, generally require high-temperature calcination, have a complicated preparation process, and are inconvenient to load bioactive drugs. Unlike traditional methods, modern 3D printing techniques use selective laser sintering to mix hydroxyapatite with low melting point substances, however, the resulting scaffolds often suffer from poor shape, require additional treatments, such as isostatic pressing, to increase density, are expensive and complex throughout the preparation process, and are difficult to load with bioactive substances.
Other 3D printing methods (photo-curing, inkjet, direct writing extrusion) typically mix hydroxyapatite powder with polymeric materials and then print the mixture by extrusion. Although direct-write extrusion 3D printing has significant advantages in biomedical fields, such as good biocompatibility and the realization of multi-material custom printing, currently available 3D printing direct-write extrusion deposition techniques generally require process steps of spraying during printing, immersing after printing, or curing with ultraviolet light. In the construction of the hydroxyapatite/polymer nano composite biological porous scaffold by 3D printing published by Liu Shuifeng of agricultural university of south China, sodium Alginate (SA), hydroxyapatite (HAP) and Glucolactone (GDL) are used as main raw materials, the sodium alginate is gelled in situ to form hydrogel serving as biological ink, the gel scaffold is obtained by an extrusion type 3D printing method, and then the scaffold is secondarily soaked in a calcium chloride solution for crosslinking so as to improve the scaffold performance. These procedures tend to result in poor structural control, low precision of the printing process, and poor mechanical properties of the stent itself due to the materials, thereby limiting the development of applications of 3D printing materials in the related art.
Therefore, it is desirable to develop a 3D printing material extruded at room temperature and a one-step molding process, which is free from biotoxicity, does not require post-crosslinking treatment, and has a three-dimensional structure with high molding accuracy, so that the material has certain application in the fields of water treatment and biomedicine.
Disclosure of Invention
Aiming at the technical problems of high equipment and material cost, complicated post-treatment procedures, potential pest toxicity risks and the like existing in various 3D printing technologies of the prior hydroxyapatite scaffold, the invention provides a room-temperature one-step 3D printing molding method of a high-precision interconnected porous structure potassium-doped hydroxyapatite/chitosan composite scaffold. The 3D printable slurry with strong injectability and moderate curing time is prepared by fully utilizing the slow release effect of potassium ions and regulating and controlling components and technological process parameters in the formula. The process can be extruded at normal temperature, does not need sintering or crosslinking post-treatment, and finally the 3D printing support material with the high-precision interconnection multi-cavity structure is obtained.
The technical scheme of the invention is as follows:
A3D printing molding method of a high-precision interconnected porous hydroxyapatite/chitosan composite scaffold at room temperature by a one-step method is characterized in that potassium-doped hydroxyapatite powder and chitosan are prepared into hydroxyapatite chitosan mixed slurry, and the hydroxyapatite chitosan mixed slurry is extruded at normal temperature to be 3D printed and self-consolidated to be molded, so that the hydroxyapatite/chitosan scaffold material is obtained.
The molar ratio of calcium, potassium and phosphorus in the potassium-doped hydroxyapatite powder is 5:3, a step of; the mass ratio of potassium in the potassium-doped hydroxyapatite powder is 10-25 wt% calculated by potassium oxide.
Wherein the potassium salt is potassium carbonate or potassium sulfate or potassium hydroxide.
The micro-morphology nano-scale of the potassium-doped hydroxyapatite powder has the length of 20-100 nm and the width of 5-10 nm.
The hydroxyapatite chitosan mixed slurry is prepared from potassium-doped hydroxyapatite powder and chitosan, and specifically comprises the following components: firstly, adding potassium-doped hydroxyapatite powder into deionized water for ultrasonic dispersion to form potassium-doped hydroxyapatite slurry; dissolving chitosan in an acetic acid solution to obtain a chitosan solution; adding the potassium-doped hydroxyapatite slurry into the chitosan solution drop by drop, and stirring in a magnetic stirrer with the temperature of 30-75 ℃ and the rotation speed of 600-1000 rpm to obtain the hydroxyapatite chitosan mixed slurry.
In the hydroxyapatite chitosan mixed slurry, the mass ratio of chitosan to potassium-doped hydroxyapatite is 1:1 to 1:2.
the deacetylation degree of the chitosan is 80-95%; the mass concentration of chitosan in the chitosan solution is 1-8%, and the mass concentration of acetic acid is 2-6%.
The stirring time is 2.5-4.5 h.
The diameter of the extrusion head for 3D printing is 0.2-1.2 mm, the height of the printed layer is 0.1-0.6 mm, the printing speed is 0.1-50 mm/s, and the printing air pressure is 30-800 kPa.
The potassium-doped hydroxyapatite is uniformly distributed in and on the surface of the interconnected porous structure.
The printing in the curing solution is not needed, the cross-linking treatment such as spraying the curing solution is also not needed, and the high-temperature treatment such as sintering is avoided. The temperature of the printing environment is kept at room temperature, and the printing environment is required to be placed on a printing substrate for 5-15 min after printing.
The invention has the beneficial effects that: the invention provides a high-precision continuous porous structure potassium-doped hydroxyapatite/chitosan composite material room-temperature one-step 3D printing forming method, which is characterized in that from the modification of hydroxyapatite, the injectability and the setting time of the obtained hydroxyapatite/chitosan composite slurry are adjustable, so that the slurry can be used for direct-writing 3D printing, and an engineering bracket with good forming and high precision is obtained.
The method specifically comprises the following aspects:
(1) The potassium-doped hydroxyapatite is introduced into a composite system, so that the injectability (more than 90 percent) and the uniformity of the slurry are obviously improved. The processing window adapting to 3D printing is provided through the regulation and control of the potassium ion release concentration in the potassium-doped hydroxyapatite and the regulation and control of the chitosan composition proportion and the process. The preparation method adopts normal-temperature one-step extrusion printing self-curing forming, does not need high-energy beam auxiliary sintering (such as laser and electron beam), does not need ultraviolet light auxiliary curing, does not need other complex post-treatment steps such as subsequent glue discharging, high-temperature sintering and the like, and provides a new and convenient way for 3D printing of the hydroxyapatite in bone tissue engineering scaffolds and water treatment.
(2) The hydroxyapatite and the chitosan adopted in the invention have high safety and good biocompatibility. The printed bone scaffold has proper porosity and pore size structure, and is favorable for bone tissue growth, so that the scaffold has excellent biocompatibility and bone conductivity. The interconnected porous structure pore structure is beneficial to nutrient substance transportation and blood vessel growth, and can promote cell attachment, proliferation and differentiation.
(3) The potassium-doped hydroxyapatite/chitosan composite scaffold material prepared by the invention is printed under the condition of about room temperature to finish 3D printing, and the low-temperature 3D printing technology is beneficial to maintenance and component affinity of the scaffold and avoids pollution. Compared with the product which needs high-temperature sintering or high-temperature printing after the same printing, the method has the advantage of higher activity.
(4) The normal-temperature one-step forming process adopted by the invention is favorable for carrying medicines and high-activity factors, and even for the affinity addition of active cells, so that the stent can have higher biological activity.
Drawings
FIG. 1 is a sample obtained in example 1. The support material can not be molded basically, is extremely easy to collapse and fuse, can not be printed basically, and can not be obtained by fusing and collapsing quickly after printing.
FIG. 2 is a sample obtained in example 2; wherein, (a) is that the obtained sample has higher precision, and (b) is that the obtained sample still has higher precision after being placed for a period of time, and the layers are distinct.
FIG. 3 is a sample obtained in example 3.
FIG. 4 is a sample obtained in example 6; wherein, (a) certain nodes for printing the sample can generate certain fusion, and the whole forming quality is good; (b) The sample is quickly collapsed and fused after being molded, and the precision is poor.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
2g of chitosan was dissolved in 3wt% (acetic acid concentration) acetic acid aqueous solution, and stirred at 60℃and 800rpm using a magnetic stirrer to prepare a 5w% concentration chitosan acetic acid solution. 3.0g of potassium-free hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment by an ultrasonic cytoclasis instrument for 10-20 minutes to be uniformly dispersed. Dropwise adding the potassium-doped hydroxyapatite suspension into chitosan acetic acid solution, wherein the mass ratio of chitosan to potassium-free hydroxyapatite is 2:3, continuing stirring for 3 hours to obtain the uniformly mixed potassium-doped hydroxyapatite chitosan suspension. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, 400kPa air pressure. The obtained sample can not be molded basically, is easy to collapse and fuse, can not be printed basically (as shown in figure 1), and can not be obtained by fusing and collapsing quickly after printing.
Example 2
2g of chitosan was dissolved in 3wt% acetic acid aqueous solution (acetic acid concentration) and vigorously stirred until clear and transparent, to prepare a 5wt% concentration chitosan gel ink. 3g of potassium-doped hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment for 10-20 minutes by using an ultrasonic cell disruption instrument, so that the potassium-doped hydroxyapatite is uniformly dispersed. Adding the potassium-doped hydroxyapatite suspension liquid drop into chitosan ink, wherein the mass ratio of chitosan to potassium-doped hydroxyapatite is 2:3, continuing stirring for 3 hours to obtain the potassium-doped hydroxyapatite chitosan composite ink. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, 400kPa air pressure. The obtained sample has higher precision, as shown in fig. 2 (a), and still has higher precision after being placed for a period of time, as shown in fig. 2 (b). And then freeze-drying to obtain the potassium-doped hydroxyapatite/chitosan composite scaffold.
Example 3
2g of chitosan was dissolved in 3wt% (acetic acid concentration) acetic acid aqueous solution, and stirred at 60℃and 800rpm using a magnetic stirrer to prepare a 5w% concentration chitosan acetic acid solution. 6g of potassium-doped hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment for 10-20 minutes by using an ultrasonic cell disruption instrument, so that the potassium-doped hydroxyapatite is uniformly dispersed. Dropwise adding the potassium-doped hydroxyapatite suspension into chitosan acetic acid solution, wherein the mass ratio of chitosan to potassium-doped hydroxyapatite is 1:3, continuing stirring for 3 hours to obtain the uniformly mixed potassium-doped hydroxyapatite chitosan suspension. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, 400kPa air pressure. As shown in fig. 3, print molding cannot be achieved.
Example 4
2.0g of chitosan was dissolved in 2wt% (acetic acid concentration) of acetic acid aqueous solution, and stirred at 60℃and 800rpm using a magnetic stirrer to prepare a 5w% concentration chitosan acetic acid solution. 4.0g of potassium-doped hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment by an ultrasonic cytoclasis instrument for 10-20 minutes to be uniformly dispersed. Dropwise adding the potassium-doped hydroxyapatite suspension into chitosan acetic acid solution, wherein the mass ratio of chitosan to potassium-doped hydroxyapatite is 1:2, continuing stirring for 3 hours to obtain the uniformly mixed potassium-doped hydroxyapatite chitosan suspension. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, and 350kPa air pressure. The obtained sample was molded completely. And then freeze-drying to obtain the potassium-doped hydroxyapatite/chitosan composite scaffold.
Example 5
2.0g of chitosan was dissolved in 2wt% (acetic acid concentration) of acetic acid aqueous solution, and stirred at 60℃and 800rpm using a magnetic stirrer to prepare a 5w% concentration chitosan acetic acid solution. 2.0g of potassium-doped hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment by an ultrasonic cytoclasis instrument for 10-20 minutes to be uniformly dispersed. Dropwise adding the potassium-doped hydroxyapatite suspension into chitosan acetic acid solution, wherein the mass ratio of chitosan to potassium-doped hydroxyapatite is 1:1, stirring for 5 hours continuously to obtain the uniformly mixed potassium-doped hydroxyapatite chitosan suspension. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, 800kPa air pressure. The obtained sample is formed completely, the smoothness in the printing process is limited to a certain extent, and the precision of the printed formed sample is high. And then freeze-drying to obtain the potassium-doped hydroxyapatite/chitosan composite scaffold.
Example 6
2g of chitosan was dissolved in 3wt% (acetic acid concentration) acetic acid aqueous solution, and stirred at 60℃and 800rpm using a magnetic stirrer to prepare a 5w% concentration chitosan acetic acid solution. 2.0g of potassium-free hydroxyapatite is mixed with deionized water, and is subjected to ultrasonic treatment by an ultrasonic cytoclasis instrument for 10-20 minutes to be uniformly dispersed. Dropwise adding the potassium-doped hydroxyapatite suspension into chitosan acetic acid solution, wherein the mass ratio of chitosan to potassium-free hydroxyapatite is 1:1, continuously stirring for 3 hours to obtain the uniformly mixed potassium-doped hydroxyapatite chitosan suspension. The composite gel ink was printed using a DIW printer under process conditions of 0.3mm diameter of the extrusion head for 3D printing, 0.3mm layer height, 30mm/s printing speed, 400kPa air pressure. Certain nodes of the printed sample are fused, and the integral forming quality is good, as shown in fig. 4 (a). The molded samples collapsed and fused very quickly with poor precision, see FIG. 4 (b).
Claims (10)
1. A high-precision interconnecting porous structure hydroxyapatite/chitosan composite scaffold room temperature one-step 3D printing forming method is characterized by comprising the following steps: preparing hydroxyapatite chitosan mixed slurry from potassium-doped hydroxyapatite powder and chitosan, extruding the hydroxyapatite chitosan mixed slurry at normal temperature, and performing 3D printing and self-solidifying forming to obtain the hydroxyapatite/chitosan scaffold material.
2. The 3D printing forming method of the high-precision interconnected porous structure hydroxyapatite/chitosan composite scaffold by a room temperature one-step method, which is characterized in that the hydroxyapatite chitosan mixed slurry is prepared from potassium-doped hydroxyapatite powder and chitosan, and specifically comprises the following steps: firstly, adding potassium-doped hydroxyapatite powder into deionized water for ultrasonic dispersion to form potassium-doped hydroxyapatite slurry; dissolving chitosan in an acetic acid solution to obtain a chitosan solution; adding the potassium-doped hydroxyapatite slurry into the chitosan solution drop by drop, and stirring in a magnetic stirrer with the temperature of 30-75 ℃ and the rotation speed of 600-1000 rpm to obtain the hydroxyapatite chitosan mixed slurry.
3. The 3D printing forming method of the high-precision interconnected porous structure hydroxyapatite/chitosan composite scaffold by a room temperature one-step method is characterized in that in the hydroxyapatite-chitosan mixed slurry, the mass ratio of chitosan to potassium-doped hydroxyapatite is 1:1 to 1:2.
4. the 3D printing forming method of the high-precision interconnected porous structure hydroxyapatite/chitosan composite scaffold by a room temperature one-step method, which is characterized in that the deacetylation degree of the chitosan is 80-95%; the mass concentration of chitosan in the chitosan solution is 1-8%, and the mass concentration of acetic acid is 2-6%.
5. The 3D printing forming method of the high-precision interconnected porous hydroxyapatite/chitosan composite scaffold according to claim 2, wherein the stirring time is 2.5-4.5 h.
6. The 3D printing forming method of the high-precision interconnected porous hydroxyapatite/chitosan composite scaffold according to any one of claims 1 to 5, wherein the diameter of an extrusion head of 3D printing is 0.2 to 1.2mm, the height of a printed layer is 0.1 to 0.6mm, the printing speed is 0.1 to 50mm/s, and the printing air pressure is 30 to 800kPa.
7. The 3D printing forming method of the high-precision interconnected porous hydroxyapatite/chitosan composite scaffold according to any one of claims 1 to 5, wherein the micro-morphology nano-scale of the potassium-doped hydroxyapatite powder is 20 to 100nm long and 5 to 10nm wide.
8. The high-precision interconnecting porous structure hydroxyapatite/chitosan composite scaffold room temperature one-step 3D printing forming method according to any one of claims 1 to 5, wherein the printing environment is room temperature, and the printing environment is placed on a printing substrate for 5 to 15 minutes after printing.
9. The 3D printing forming method of the high-precision interconnected porous hydroxyapatite/chitosan composite scaffold according to any one of claims 1 to 5, wherein the molar ratio of calcium+potassium to phosphorus in the potassium-doped hydroxyapatite powder is 5:3, a step of; the mass ratio of potassium in the potassium-doped hydroxyapatite powder is 10-25 wt% calculated by potassium oxide.
10. The 3D printing and forming method of the hydroxyapatite/chitosan composite scaffold with the high-precision interconnection porous structure according to claim 9, wherein the potassium salt is potassium carbonate or potassium sulfate or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410022244.3A CN117800655A (en) | 2024-01-08 | 2024-01-08 | High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410022244.3A CN117800655A (en) | 2024-01-08 | 2024-01-08 | High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117800655A true CN117800655A (en) | 2024-04-02 |
Family
ID=90430148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410022244.3A Pending CN117800655A (en) | 2024-01-08 | 2024-01-08 | High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117800655A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118178719A (en) * | 2024-05-20 | 2024-06-14 | 贝兴悦(成都)科技有限公司 | Hydroxyapatite composite hydrogel and preparation method and application thereof |
-
2024
- 2024-01-08 CN CN202410022244.3A patent/CN117800655A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118178719A (en) * | 2024-05-20 | 2024-06-14 | 贝兴悦(成都)科技有限公司 | Hydroxyapatite composite hydrogel and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Review of 3D printable hydrogels and constructs | |
| CN117800655A (en) | High-precision interconnecting porous hydroxyapatite/chitosan composite stent room-temperature one-step 3D printing forming method | |
| Ozkoc et al. | Production of poly (lactic acid)/organoclay nanocomposite scaffolds by microcompounding and polymer/particle leaching | |
| Xu et al. | Chitosan-based high-strength supramolecular hydrogels for 3D bioprinting | |
| CN110685038B (en) | Core/shell composite fiber and preparation method thereof | |
| CN112206353B (en) | Chitin whisker liquid crystal elastomer modified polylactic acid composite material and preparation method and application thereof | |
| CN109809811A (en) | A kind of bioactive ceramics bracket of Nano/micron hierarchical porous structure and preparation method thereof | |
| CN115042428A (en) | Additive manufacturing method for constructing multiple continuous gradient functional bone scaffold | |
| CN107456602A (en) | A kind of medical aquogel body dressing of the short fine enhancing of full biodegradable and preparation method thereof | |
| US8431623B2 (en) | Process for forming a porous PVA scaffold using a pore-forming agent | |
| CN105963789A (en) | Method for preparing bone tissue engineering scaffold material | |
| CN113651916A (en) | Mineralized hydrogel and preparation method and application thereof | |
| EP1712343A1 (en) | Method of producing a composite article by Solid Freefrom manufacturing | |
| CN110680954A (en) | 3D printing xanthan gum hydrogel support and preparation method thereof | |
| Maher et al. | Formed 3D bio-scaffolds via rapid prototyping technology | |
| CN116118177B (en) | 3D printing hydrogel stent based on high molecular weight regenerated silk fibroin and preparation method thereof | |
| CN113103576B (en) | 3D printing method for ordered gradient porous material | |
| CN112957522B (en) | Rigidity-adjustable porous liquid metal bone tissue engineering scaffold and preparation method thereof | |
| Mania et al. | Review of current research on chitosan as a raw material in three-dimensional printing technology in biomedical applications | |
| CN114470336A (en) | Co-extrusion and co-molding mixed hydrogel and 3D printing method of hydrogel support | |
| Lu et al. | Novel methods to fabricate macroporous 3D carbon scaffolds and ordered surface mesopores on carbon filaments | |
| CN111808474A (en) | Preparation method of biological 3D printing ink based on nanocellulose | |
| CN115120779B (en) | Hydrogel foam material for 3D printing and preparation method and application thereof | |
| CN114957766B (en) | Preparation method of graphical porous hydrogel film | |
| Barakat | 3D printing of hydrogels and nanoparticle containing bio-inks for bone tissue regeneration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |