CN111805686A - Method for improving degradability of 3D gel printing calcium phosphate ceramic support - Google Patents
Method for improving degradability of 3D gel printing calcium phosphate ceramic support Download PDFInfo
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- CN111805686A CN111805686A CN202010580529.0A CN202010580529A CN111805686A CN 111805686 A CN111805686 A CN 111805686A CN 202010580529 A CN202010580529 A CN 202010580529A CN 111805686 A CN111805686 A CN 111805686A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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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
- B33Y10/00—Processes of additive manufacturing
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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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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Abstract
The invention relates to a method for improving degradability of a 3D gel printing calcium phosphate ceramic support, and belongs to the field of advanced and rapid 3D printing manufacturing. The method comprises the steps of improving the magnesium content in calcium magnesium phosphate by changing the adding sequence of reactants, mixing self-made calcium magnesium phosphate powder and premixed liquid to prepare ceramic slurry which is high in stability, low in viscosity and suitable for printing, printing by adopting an autonomously designed 3D gel printer, obtaining a ceramic part in a complex shape by adjusting printing parameters such as the diameter of a spray head, the height of a printing layer, air pressure and printing speed, drying, degreasing and sintering a printing blank to obtain a ceramic part sintered body, immersing the sintered ceramic part into simulated body fluid, and representing the influence of different magnesium contents on the degradation of a bracket by measuring the weight loss rate of the bracket in the simulated body fluid. The method can be used for preparing ceramic biological products with complex shapes, good mechanical properties and good degradability.
Description
Technical Field
The invention relates to a method for improving the degradability of a 3D gel printing calcium phosphate ceramic support, and belongs to the field of advanced rapid manufacturing.
Background
The 3D printing technology, also known as additive manufacturing technology, is a rapid prototyping technology developed on the basis of 2D printing, microdrop spraying and modern materials science, and the basic principle is that based on a digital model file, adhesive materials such as powdered metal or ceramic are bonded with each other layer by layer through printing layer by layer to form a three-dimensional model of a real object. The 3D gel-Printing (3 DGP) technology is a novel 3D Printing and forming technology based on a Slurry Printing technology (S-3 DPTM) or a Direct Inkjet Printing technology (DIP), where the Printing Slurry is composed of a ceramic or metal Slurry with a relatively low viscosity and a relatively high solid volume fraction content, the printer sprays the Slurry onto a Printing platform, and at the same time, an organic monomer in the Slurry is initiated to perform a radical polymerization reaction in a very short time in a certain manner, and a Three-dimensional network-structured polymer organic matter coats powder particles in situ, so that the Slurry is rapidly cured and formed, and after the Slurry is printed, cured and formed layer by layer, a part blank is formed, and the blank is degreased and sintered, and a compact part is finally obtained.
The tricalcium phosphate component is similar to the inorganic component of the bone tissue, and under the condition of steady internal environment, the tricalcium phosphate has higher binding force with the bone tissue, has good biological safety and no obvious rejection reaction, and can smoothly realize the deposition and the material exchange of calcium salt when new bones grow into the bracket. However, tricalcium phosphate has poor resistance to external impacts and does not completely match the rate of degradation to the rate of new bone formation. The addition of the magnesium element in the self-made calcium magnesium phosphate powder can not only improve the compressive strength of the tricalcium phosphate support, but also improve the degradation rate of the tricalcium phosphate support in simulated body fluid, so that the material can be dissolved, absorbed or discharged from the body in a metabolism process step by step, the bone defect part is replaced by new bone tissues, and the degraded calcium and phosphorus ions can enter a human body circulatory system and gradually form new bones. In addition, in the process of preparing the calcium magnesium phosphate powder, the magnesium content in the product can be improved by changing the adding sequence of reactants, so that the accurate control of the degradability of the material is realized.
The method for changing the adding sequence of the reactants is utilized to improve the magnesium content in the calcium magnesium phosphate, thereby not only solving the defect of high brittleness of calcium phosphate, but also improving the degradability of the calcium phosphate. Meanwhile, the ceramic part formed by the 3D gel printing technology not only solves the problem that the ceramic is difficult to form, but also can realize near-net forming of a complex ceramic part, and saves cost.
In the invention, the ceramic support sintered after printing is soaked in simulated body fluid, and the influence of different magnesium contents on the degradability of the support is represented by detecting the weight loss rate of the support in the simulated body fluid.
Disclosure of Invention
The invention aims to provide a simple method for increasing the magnesium content in powder, and then a calcium phosphate magnesium part with a complex shape and a near net shape is manufactured in a low-cost and high-efficiency mode, so that a biological implantation part with excellent degradability, mechanical property and biocompatibility is obtained.
The principle of the invention is as follows: firstly, preparing calcium chloride solution, diammonium phosphate solution and magnesium chloride hexahydrate solution with different calcium-phosphorus ratios, and then changing the adding sequence of the calcium chloride solution and the magnesium chloride hexahydrate solution to prepare calcium phosphate-magnesium powder with different magnesium contents. And then adding the prepared calcium phosphate magnesium powder into the premixed liquid, preparing calcium phosphate magnesium slurry with a certain solid content, then loading the prepared calcium phosphate magnesium slurry into an independently designed 3D gel printer for printing, adjusting printing parameters such as the diameter of a spray head, the height of a printing layer, the extrusion rate, the printing speed and the like in the printing process to obtain a printing blank body with good surface quality and a complex shape, and degreasing and sintering the printing blank body to obtain the ceramic support. And then the obtained ceramic support is soaked in simulated body fluid, so that the degradation rate of the support printed by the powder with higher magnesium content in the simulated body fluid is higher, and the degradability of the support is improved.
Based on the above principle and purpose, the process of the present invention comprises: the method comprises the steps of preparing calcium phosphate magnesium powder with different magnesium contents, preparing printing slurry, setting printing parameters, printing 3D gel, degreasing and sintering a printing blank, testing in-vitro degradability and the like. The specific process comprises the following steps:
a method for improving degradability of a 3D gel printing calcium phosphate ceramic support comprises the following specific steps:
(1) respectively preparing an anhydrous calcium chloride aqueous solution, a diammonium hydrogen phosphate aqueous solution and a magnesium chloride hexahydrate aqueous solution with the concentration of 0.02-0.8 mol/L for later use;
(2) under the temperature condition of 0-60 ℃, adding a magnesium chloride hexahydrate aqueous solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, and then adding an anhydrous calcium chloride aqueous solution to obtain a mixed solution A; then changing the adding sequence of the magnesium chloride hexahydrate solution and the anhydrous calcium chloride, namely adding the anhydrous calcium chloride aqueous solution into the diammonium hydrogen phosphate aqueous solution for uniform mixing, and then adding the magnesium chloride hexahydrate aqueous solution to obtain a mixed solution B;
(3) aging the mixed solution A and B obtained in the step (2) for 9-18 h respectively, filtering to obtain precipitates, washing the precipitates to be neutral by using distilled water and ethanol alternately, and drying the washed precipitates at 30-90 ℃ to obtain calcium magnesium phosphate powder A1 and B1 under different reactant adding sequences;
(4) dissolving 0.5-4 wt% of a dispersing agent, 0.1-0.5 wt% of an emulsifying agent and 0.5-1 wt% of a curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed solution according to the volume ratio of (0.5-2): 1, and uniformly stirring to obtain calcium magnesium phosphate slurry A2 and B2 with the solid content of 35-67 vol% and the viscosity of 200-800 Pa.s;
(5) respectively loading the calcium phosphate magnesium slurry A2 and the B2 obtained in the step (4) into a needle cylinder of A3D gel printer, guiding the shape of a product to be printed into a computer control system for printing, and printing the obtained blanks A3 and B3, wherein the diameter of a spray head selected for printing is 0.1-0.5 mm, the height of a printing layer is 0.1-0.7 mm, the printing pressure is 0.1-0.6 MPa, and the printing speed is 5-25 mm/s;
(6) drying the printed green bodies A3 and B3 at 25-50 ℃ for 24-48 h, degreasing the dried green bodies at 30-90 ℃ for 3-8 h to completely decompose and volatilize organic matters, and sintering at 800-1000 ℃ for 1-3 h to obtain calcium magnesium phosphate supports A4 and B4;
(7) soaking the scaffolds A4 and B4 obtained in the step (6) in simulated body fluid, and measuring the weight loss rate of the scaffold in the simulated body fluid to be not less than 12% in 12 weeks.
Further, the molar ratio of (Ca + Mg)/P in the anhydrous calcium chloride aqueous solution, the diammonium phosphate aqueous solution and the magnesium chloride hexahydrate aqueous solution in the step (2) is 1.50-1.56, and the molar ratio of Mg/Ca is 0.2-0.7.
Further, the average particle size of the calcium magnesium phosphate powder in the step (3) is 5-30 μm.
Further, uniformly mixing the calcium magnesium phosphate powder obtained in the step (3) and the premix according to a certain volume ratio, wherein if the ratio is too large, the solid content of the slurry is too high, and the fluidity of the slurry is reduced to influence the printing quality; on the contrary, if the proportion is too small, the solid content of the slurry is low, and the mechanical property of the printing blank body is reduced. According to the previous experimental study, calcium magnesium phosphate powder and the premix are mixed according to the volume ratio (0.5-2) to 1, and the calcium magnesium phosphate slurry which is suitable for gel printing and has the solid phase content of 35-67 vol% and the viscosity of 200-800 Pa.s can be obtained by uniformly stirring.
Further, the calcium magnesium phosphate powder obtained in the step (3) has obviously improved degradability in-vitro simulated body fluid of the printed ceramic stent along with the increase of the magnesium content.
Further, the dispersant in the step (4) is one of polyvinyl alcohol, polylactic acid, polyethylene glycol, sodium hexametaphosphate, sodium tripolyphosphate, CMC and sodium polyacrylate.
Further, the emulsifier in the step (4) is one of oleic acid, polyacrylamide, monoglyceride, fatty acid ester, sodium alkyl benzene sulfonate, sodium dodecyl sulfate, N-dodecyl dimethylamine, octadecyl alkyl benzene sulfonate, dimethyl benzene naphthalene sulfonate and sodium stearate; the adopted curing mode is physical curing and chemical curing, the physical curing mode is peripheral thermosetting, and the chemical curing agent is one of citric acid, polyamide, aliphatic amine and alicyclic amine.
Further, the mass fractions of the dispersing agent, the emulsifying agent and the curing agent in the step (4) are 0.5-4 wt% of the dispersing agent, 0.1-0.5 wt% of the emulsifying agent and 0.5-1 wt% of the curing agent respectively.
The bracket printed by the calcium phosphate magnesium powder prepared by different adding sequences is in simulated body fluid
The degradability is different.
The invention provides a method for improving the degradability of A3D gel printing calcium phosphate ceramic stent, which comprises the steps of obtaining calcium phosphate magnesium powder A, B with different magnesium contents by changing the adding sequence of reactants, preparing 3D gel printing slurry A1 and B1 with high stability and low viscosity by using the two powders respectively, carrying out 3D gel printing, and then soaking sintered calcium phosphate magnesium workpieces A4 and B4 in simulated body fluid respectively to determine the degradation rate of the workpieces, so that the magnesium content in the calcium phosphate magnesium powder is improved by changing the adding sequence of the reactants, the degradation speed of the stent in the simulated body fluid is finally improved, the process is simple, the near-net forming of the ceramic workpieces with good degradability is realized, and the production cost is saved.
The ceramic bracket formed by the process has the advantages that: the method for changing the adding sequence of reactants is utilized to improve the magnesium content in the self-made calcium magnesium phosphate powder, not only maintains the good biocompatibility of calcium phosphate, but also improves the mechanical property and degradability of the calcium phosphate by adding magnesium ions, and solves the defects of poor mechanical property and slow degradation speed of the calcium phosphate. Secondly, the main components of the material are close to human bones, so that the biocompatibility of the product is further improved; on the other hand, the ceramic support prepared by the 3D gel printing technology overcomes the defect that ceramics are difficult to form by using the traditional method, and realizes the near-net forming of complex ceramic biological products.
Detailed Description
The invention provides a simple method for improving the magnesium content in the powder, and then a calcium phosphate magnesium part with a complex shape and a near net shape is manufactured in a low-cost and high-efficiency mode, so that a biological implantation part with excellent degradability, mechanical property and biocompatibility is obtained.
The process of the present invention comprises: the method comprises the steps of preparing calcium phosphate magnesium powder with different magnesium contents, preparing printing slurry, setting printing parameters, printing 3D gel, degreasing and sintering a printing blank, testing in-vitro degradability and the like. The specific process comprises the following steps:
(1) respectively preparing an anhydrous calcium chloride aqueous solution, a diammonium hydrogen phosphate aqueous solution and a magnesium chloride hexahydrate aqueous solution with the concentration of 0.02-0.8 mol/L for later use;
(2) under the temperature condition of 0-60 ℃, adding a magnesium chloride hexahydrate aqueous solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, then adding an anhydrous calcium chloride aqueous solution into the mixed solution, and stirring while adding to obtain a mixed solution A; then changing the adding sequence of the magnesium chloride hexahydrate solution and the anhydrous calcium chloride, namely adding the anhydrous calcium chloride aqueous solution into the diammonium hydrogen phosphate aqueous solution for uniform mixing, then adding the magnesium chloride hexahydrate aqueous solution into the mixed solution, and stirring while adding to obtain a mixed solution B;
(3) aging the mixed solution A and B obtained in the step (2) for 9-18 h respectively, filtering to obtain precipitates, washing the precipitates to be neutral by using distilled water and ethanol alternately, and drying the washed precipitates at 30-90 ℃ to obtain calcium magnesium phosphate powder A1 and B1 under different reactant adding sequences;
the initial concentration of the solution in step (1), the temperature conditions in step (2), the addition sequence of solutions a and B, and the aging time and drying temperature in step (3) are all critical processes that are integrated to ensure that the resulting magnesium calcium phosphate powder has the correct shape (spherical or near-spherical), average particle size (D50 ═ 80-120nm), and particle size distribution (particle size distribution D10 greater than 20nm, D90 less than 180nm) to allow the subsequent slurry to have the correct rheological behavior for the 3D gel printing process. In addition, the densification can be ensured at a lower temperature in the subsequent sintering process, and the required mechanical property of the stent can be obtained. The effect of the invention can be achieved only by combining the processes, and the effect cannot be achieved by changing a variable independently.
(4) Dissolving 0.5-4 wt% of a dispersing agent, 0.1-0.5 wt% of an emulsifying agent and 0.5-1 wt% of a curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed solution according to the volume ratio of (0.5-2): 1, and uniformly stirring to obtain calcium magnesium phosphate slurry A2 and B2 with the solid content of 35-67 vol% and the viscosity of 200-800 Pa.s;
(5) respectively loading the calcium phosphate magnesium slurry A2 and the calcium phosphate magnesium slurry B2 obtained in the step (4) into a needle cylinder of a 3D gel printer which is independently developed, and guiding the shape of a product to be printed into a computer control system for printing, wherein the diameter of a spray head selected for printing is 0.1-0.5 mm, the height of a printing layer is 0.1-0.9 mm, the printing pressure is 0.1-0.6 MPa, and the printing speed is 5-25 mm/s;
(6) drying the printed green bodies A3 and B3 at 25-50 ℃ for 24-48 h, degreasing the dried green bodies at 30-90 ℃ for 3-8 h to completely decompose and volatilize organic matters, and sintering at 800-1100 ℃ for 1-3 h to obtain calcium magnesium phosphate supports A4 and B4;
(7) soaking the scaffolds A4 and B4 obtained in the step (6) in simulated body fluid, and measuring the weight loss rate of the scaffold in the simulated body fluid to be not less than 12% in 12 weeks.
Example 1: preparation of calcium magnesium phosphate ceramic bracket with magnesium content of 2% by 3D gel printing
1) Weighing 14.7g of diammonium hydrogen phosphate, 18.24g of anhydrous calcium chloride and 1.23g of magnesium chloride hexahydrate, respectively dissolving in 200ml of distilled water to obtain respective aqueous solutions, and measuring the pH value;
2) under the temperature condition of 30 ℃, firstly, adding an anhydrous calcium chloride solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, then adding a magnesium chloride hexahydrate aqueous solution into the mixed solution, and stirring while adding to obtain a mixed solution;
3) respectively aging the mixed solution obtained in the step (2) for 9h, filtering to obtain a precipitate, alternately washing the precipitate to be neutral by using distilled water and ethanol, and drying the washed precipitate at 30 ℃ to prepare calcium magnesium phosphate powder;
4) dissolving 0.5 wt% of dispersing agent, 0.2 wt% of emulsifying agent and 0.6 wt% of curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, then mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed solution according to the volume ratio of 0.8:1, and uniformly stirring to obtain ceramic slurry with the solid phase content of 45 vol% and the viscosity of 720 Pa.s;
5) filling the calcium phosphate magnesium slurry obtained in the step (4) into a needle cylinder of a 3D gel printer which is independently researched and developed, and guiding the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.2mm, the height of a printing layer is 0.18mm, the printing pressure is 0.2MPa, and the printing speed is 15 mm/s;
6) drying the printed blank body at 30 ℃ for 20h, degreasing the dried blank body at 500 ℃ for 4h to completely decompose and volatilize organic matters, and sintering at 800 ℃ for 1.5h to obtain a ceramic support;
7) and (4) soaking the stent obtained in the step (6) in simulated body fluid, wherein the weight loss rate of the stent in the simulated body fluid is 12% after 12 weeks.
Example 2: preparation of calcium magnesium phosphate ceramic bracket with magnesium content of 6% by 3D gel printing
1) Weighing 16.28g of diammonium hydrogen phosphate, 17.54g of anhydrous calcium chloride and 6.76g of magnesium chloride hexahydrate, respectively dissolving in 200ml of distilled water to obtain respective aqueous solutions, and measuring the pH value;
2) under the temperature condition of 20 ℃, firstly, adding an anhydrous calcium chloride solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, then adding a magnesium chloride hexahydrate aqueous solution into the mixed solution, and stirring while adding to obtain a mixed solution;
3) respectively aging the mixed solution obtained in the step (2) for 15h, filtering to obtain a precipitate, alternately washing the precipitate to neutrality by using distilled water and ethanol, and drying the washed precipitate at 50 ℃ to prepare calcium magnesium phosphate powder;
4) dissolving 4 wt% of dispersing agent, 0.1 wt% of emulsifying agent and 0.9 wt% of curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, then mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed solution according to the volume ratio of 1:1, and uniformly stirring to obtain ceramic slurry with the solid phase content of 35 vol% and the viscosity of 500 Pa.s;
5) filling the calcium phosphate magnesium slurry obtained in the step (4) into a needle cylinder of a 3D gel printer which is independently researched and developed, and guiding the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1mm, the height of a printing layer is 0.13mm, the printing pressure is 0.3MPa, and the printing speed is 10 mm/s;
6) drying the printed green body at 50 ℃ for 24h, degreasing the dried green body at 400 ℃ for 4h to completely decompose and volatilize organic matters, and sintering at 1000 ℃ for 2h to obtain a ceramic support;
7) and (4) soaking the stent obtained in the step (6) in simulated body fluid, wherein the weight loss rate of the stent in the simulated body fluid is 16% after 12 weeks.
Example 3: preparation of calcium magnesium phosphate ceramic bracket with 10% magnesium content by 3D gel printing
1) Weighing 14.93g of diammonium hydrogen phosphate, 15.98g of anhydrous calcium chloride and 6.14g of magnesium chloride hexahydrate, respectively dissolving in 200ml of distilled water to obtain respective aqueous solutions, and measuring the pH value;
2) under the temperature condition of 50 ℃, firstly adding a magnesium chloride hexahydrate aqueous solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, then adding an anhydrous calcium chloride aqueous solution into the mixed solution, and stirring while adding to obtain a mixed solution;
3) respectively aging the mixed solution obtained in the step (2) for 18h, filtering to obtain a precipitate, alternately washing the precipitate to neutrality by using distilled water and ethanol, and drying the washed precipitate at 90 ℃ to prepare calcium magnesium phosphate powder;
4) dissolving 1 wt% of dispersing agent, 0.3 wt% of emulsifying agent and 1 wt% of curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed liquid, then mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed liquid according to the volume ratio of 2:1, and uniformly stirring to obtain ceramic slurry with the solid phase content of 55 vol% and the viscosity of 756 Pa.s;
5) filling the calcium phosphate magnesium slurry obtained in the step (4) into a needle cylinder of a 3D gel printer which is independently researched and developed, and guiding the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.3mm, the height of a printing layer is 0.24mm, the printing pressure is 0.4MPa, and the printing speed is 8 mm/s;
6) drying the printed blank body at 80 ℃ for 48h, degreasing the dried blank body at 600 ℃ for 6h to completely decompose and volatilize organic matters, and sintering at 1100 ℃ for 3h to obtain a ceramic support;
7) and (4) soaking the stent obtained in the step (6) in simulated body fluid, wherein the weight loss rate of the stent in the simulated body fluid is 23% after 12 weeks.
Comparative example 1: preparation of calcium phosphate ceramic bracket without adding magnesium by 3D gel printing
1) Weighing 13.62g of diammonium hydrogen phosphate and 17.28g of anhydrous calcium chloride, respectively dissolving in 200ml of distilled water to obtain respective aqueous solutions, and measuring the pH value;
2) under the temperature condition of 40 ℃, adding an anhydrous calcium chloride solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, and stirring while adding to obtain a mixed solution;
3) aging the mixed solution obtained in the step (2) for 12h respectively, filtering to obtain precipitates, washing the precipitates to be neutral by using distilled water and ethanol alternately, and drying the washed precipitates at 60 ℃ to prepare calcium phosphate powder;
4) dissolving 3.5 wt% of dispersing agent, 0.15 wt% of emulsifying agent and 0.7 wt% of curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, then mixing the ceramic powder obtained in the step (3) and the premixed solution according to the volume ratio of 0.5:1, and uniformly stirring to obtain ceramic slurry with the solid phase content of 30 vol% and the viscosity of 550 Pa.s;
5) filling the calcium phosphate magnesium slurry obtained in the step (4) into a needle cylinder of a 3D gel printer which is independently researched and developed, and guiding the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.4mm, the height of a printing layer is 0.72mm, the printing pressure is 0.5MPa, and the printing speed is 6 mm/s;
6) drying the printed blank body at 70 ℃ for 12h, degreasing the dried blank body at 450 ℃ for 6h to completely decompose and volatilize organic matters, and sintering at 1050 ℃ for 1h to obtain a ceramic support;
7) and (4) soaking the stent obtained in the step (6) in simulated body fluid, wherein the weight loss rate of the stent in the simulated body fluid is 7% after 12 weeks.
By comparison, the calcium phosphate magnesium stent obtained by adding magnesium improves the degradation rate of the stent in simulated body fluid.
Claims (7)
1. A method for improving degradability of a 3D gel-printed calcium phosphate ceramic support is characterized by comprising the following specific steps:
(1) respectively preparing an anhydrous calcium chloride aqueous solution, a diammonium hydrogen phosphate aqueous solution and a magnesium chloride hexahydrate aqueous solution with the concentration of 0.02-0.8 mol/L for later use;
(2) under the temperature condition of 0-60 ℃, adding a magnesium chloride hexahydrate aqueous solution into a diammonium hydrogen phosphate aqueous solution for uniform mixing, and then adding an anhydrous calcium chloride aqueous solution to obtain a mixed solution A; then changing the adding sequence of the magnesium chloride hexahydrate solution and the anhydrous calcium chloride, namely adding the anhydrous calcium chloride aqueous solution into the diammonium hydrogen phosphate aqueous solution for uniform mixing, and then adding the magnesium chloride hexahydrate aqueous solution to obtain a mixed solution B;
(3) aging the mixed solution A and B obtained in the step (2) for 9-18 h respectively, filtering to obtain precipitates, washing the precipitates to be neutral by using distilled water and ethanol alternately, and drying the washed precipitates at 30-90 ℃ to obtain calcium magnesium phosphate powder A1 and B1 under different reactant adding sequences;
(4) dissolving 0.5-4 wt% of a dispersing agent, 0.1-0.5 wt% of an emulsifying agent and 0.5-1 wt% of a curing agent in distilled water, continuously stirring by using a glass rod until the dispersing agent, the emulsifying agent and the curing agent are completely dissolved to obtain a premixed solution, mixing the calcium magnesium phosphate powder obtained in the step (3) and the premixed solution according to the volume ratio of (0.5-2): 1, and uniformly stirring to obtain calcium magnesium phosphate slurry A2 and B2 with the solid content of 35-67 vol% and the viscosity of 200-800 Pa.s;
(5) respectively loading the calcium phosphate magnesium slurry A2 and the B2 obtained in the step (4) into a needle cylinder of A3D gel printer, guiding the shape of a product to be printed into a computer control system for printing, and printing the obtained blanks A3 and B3, wherein the diameter of a spray head selected for printing is 0.1-0.5 mm, the height of a printing layer is 0.1-0.7 mm, the printing pressure is 0.1-0.6 MPa, and the printing speed is 5-25 mm/s;
(6) drying the printed green bodies A3 and B3 at 25-50 ℃ for 24-48 h, degreasing the dried green bodies at 30-90 ℃ for 3-8 h to completely decompose and volatilize organic matters, and sintering at 800-1000 ℃ for 1-3 h to obtain calcium magnesium phosphate supports A4 and B4;
(7) soaking the scaffolds A4 and B4 obtained in the step (6) in simulated body fluid, and measuring the weight loss rate of the scaffold in the simulated body fluid to be not less than 12% in 12 weeks.
2. The method of claim 1, wherein the method comprises the following steps: the molar ratio of (Ca + Mg)/P in the anhydrous calcium chloride aqueous solution, the diammonium phosphate aqueous solution and the magnesium chloride hexahydrate aqueous solution in the step (2) is 1.50-1.56, and the molar ratio of Mg/Ca is 0.2-0.7.
3. The method of claim 1, wherein the method comprises the following steps: and (4) the average particle size of the calcium phosphate magnesium powder in the step (3) is 5-30 mu m.
4. The method of claim 1, wherein the method comprises the following steps: the dispersant in the step (4) is one of polyvinyl alcohol, polylactic acid, polyethylene glycol, sodium hexametaphosphate, sodium tripolyphosphate, CMC and sodium polyacrylate.
5. The method of claim 1, wherein the method comprises the following steps: the emulsifier in the step (4) is one of oleic acid, polyacrylamide, mono-diglyceride, fatty acid ester, sodium alkyl benzene sulfonate, sodium dodecyl sulfate, N-dodecyl dimethylamine, octadecyl alkyl benzene sulfonate, dimethyl benzene sulfonate and sodium stearate; the adopted curing mode is physical curing and chemical curing, the physical curing mode is peripheral thermosetting, and the chemical curing agent is one of citric acid, polyamide, aliphatic amine and alicyclic amine.
6. The method of claim 1, wherein the method comprises the following steps: the mass fractions of the dispersing agent, the emulsifying agent and the curing agent in the step (4) are 0.5-4 wt% of the dispersing agent, 0.1-0.5 wt% of the emulsifying agent and 0.5-1 wt% of the curing agent respectively.
7. The method of claim 1, wherein the method comprises the following steps: the degradation of the bracket printed by the calcium phosphate magnesium powder prepared by different adding sequences in simulated body fluid is different.
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