CN111635224A - Mg and Zn doped tricalcium phosphate material, 3D printing ceramic slurry and preparation method thereof - Google Patents

Mg and Zn doped tricalcium phosphate material, 3D printing ceramic slurry and preparation method thereof Download PDF

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CN111635224A
CN111635224A CN202010529753.7A CN202010529753A CN111635224A CN 111635224 A CN111635224 A CN 111635224A CN 202010529753 A CN202010529753 A CN 202010529753A CN 111635224 A CN111635224 A CN 111635224A
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tricalcium phosphate
phosphate material
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CN111635224B (en
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曹磊
张兴
白芸
杨锐
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Institute of Metal Research of CAS
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Abstract

The invention relates to a tricalcium phosphate material doped with Mg and Zn, 3D printing ceramic slurry and a preparation method thereof. The main technical scheme adopted is as follows: in the Mg and Zn doped tricalcium phosphate material: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. The sum of the mole numbers of Mg and Zn is n3(ii) a Wherein n is1/n310-15%; n is2/n3Is 5-10%. The 3D printing ceramic slurry comprises ceramic powder and an organic resin solution; wherein, the ceramic powder is the tricalcium phosphate material doped with Mg and Zn. The invention mainly improves the bioactivity of the tricalcium phosphate material by doping Mg and Zn elements; the tricalcium phosphate material doped with Mg and Zn is used as ceramic powder in the 3D printing ceramic slurry, so that the biological activity and compactness of the biological ceramic prepared by 3D printing can be improved.

Description

Mg and Zn doped tricalcium phosphate material, 3D printing ceramic slurry and preparation method thereof
Technical Field
The invention relates to the technical field of biological ceramic materials, in particular to a tricalcium phosphate material doped with Mg and Zn, 3D printing ceramic slurry and a preparation method thereof.
Background
The bone defect repair is one of the common clinical symptoms of orthopedics, and only about 300 ten thousand patients with bone defects or bone injuries caused by various accidents and diseases in China every year. Small-area bone defects can be cured by means of the self-regeneration function of the body; larger areas of bone defects cannot be repaired by themselves, and if not treated, may cause "nonunion", thus requiring the use of implanted artificial bone material to assist in bone tissue repair and healing. Artificial bone materials (e.g., tricalcium phosphate ceramics, bone cement, and high molecular weight polymers) are increasingly used in clinical bone defect repair. Wherein, the tricalcium phosphate has good biocompatibility and can be finally degraded after being implanted in vivo, thus being an ideal third-generation degradable biological ceramic.
The 3D printing technology can prepare multifunctional ceramics with complex structure and high precision, so the 3D printing technology can be used for preparing biological ceramics (such as artificial bones). The photocuring ceramic 3D printing technology has the advantages of high precision, flexible process and the like, and has a good application prospect. The ceramic slurry is the core technology of photocuring ceramic 3D printing.
At present, ceramic powder in the 3D printing ceramic slurry is traditional calcium phosphate (undoped), alumina, zirconia and other materials, and the particle size of the ceramic powder is submicron (0.7-1.5 μm). However, the inventors of the present invention have found that the ceramic powder used in the conventional 3D printing has at least the following technical problems: (1) the biological activity of the traditional calcium phosphate material, alumina, zirconia and other materials is low, and the biological ceramic prepared by using the traditional calcium phosphate material, alumina, zirconia and other materials as ceramic powder for 3D printing is low, cannot promote the growth of bones and is too slow; (2) the preparation method of the nano ceramic powder is complex and has high energy consumption.
Disclosure of Invention
In view of the above, the present invention provides a tricalcium phosphate material doped with Mg and Zn, a 3D printing ceramic slurry and a preparation method thereof, and mainly aims to improve the bioactivity of the tricalcium phosphate material by doping magnesium and zinc to prepare a bioceramic (e.g., artificial bone) with good bioactivity.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a Mg and Zn doped tricalcium phosphate material, wherein, in the Mg and Zn doped tricalcium phosphate material: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. The sum of the mole numbers of Mg and Zn is n3(ii) a Wherein n is1/n310-15%; n is2/n3Is 5-10%.
Preferably, the particle size of the Mg and Zn doped tricalcium phosphate material is 30-150 nm.
On the other hand, the preparation method of the Mg and Zn doped tricalcium phosphate material comprises the following steps: 1) reacting a first solution containing magnesium ions, zinc ions and calcium ions with a second solution containing phosphate ions at a set temperature for a set time to obtain a reaction product;
wherein in the first solution: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. The sum of the mole numbers of Mg and Zn is n3(ii) a Wherein n is1/n310-15%; n is2/n35-10%;
2) and after cleaning the reaction product, carrying out freeze-drying or drying treatment to obtain the Mg and Zn doped tricalcium phosphate material.
Preferably, in the step 1): setting the time to be 6-24 h; and/or the set temperature is 80-160 ℃.
Preferably, in the step 1): the first solution is a mixed solution of calcium salt, magnesium salt and zinc salt; preferably, the first solution is a mixed solution of calcium nitrate, magnesium nitrate and zinc nitrate; further preferably, in the first solution: the concentration of calcium nitrate is 100-200g/L, the concentration of magnesium nitrate is 10-40g/L, and the concentration of zinc nitrate is 10-30 g/L.
Preferably, in the step 1): the second solution is ammonium dihydrogen phosphate solution with the pH value adjusted by ammonia water; preferably, the concentration of the ammonium dihydrogen phosphate is 25-100 g/L; preferably, the pH value of the second solution is 8.5-9.5; preferably, the mass fraction of the ammonia water is 20 to 30 wt%, preferably 25 wt%.
Preferably, in the step 1): the volume ratio of the first solution to the second solution (1: 1.2) - (1.2: 1), preferably (1: 1.1) - (1.1: 1), and more preferably 1: 1; and/or the mole number of the phosphorus element in the second solution is n4(ii) a Wherein n is3/n4Is 1.45-1.65, preferably 1.5.
Preferably, the step 1) is specifically: adding the first solution into the second solution, and reacting the first solution and the second solution at a set temperature for a set time under the condition of stirring.
On the other hand, the embodiment of the invention also provides 3D printing ceramic slurry, wherein the ceramic powder in the 3D printing ceramic slurry is the above-mentioned tricalcium phosphate material doped with Mg and Zn; preferably, the 3D printing ceramic slurry comprises ceramic powder and an organic resin solution; wherein the volume fraction of the ceramic powder is 30-60%, and the volume fraction of the organic resin is 40-70%; preferably, the organic resin solution includes: 92-98.7 percent of light-cured resin by volume fraction, 0.1-1 percent of photoinitiator by volume fraction, 0.1-1 percent of flatting agent by volume fraction, 0.1-1 percent of defoaming agent by volume fraction and 1-5 percent of dispersant by volume fraction.
On the other hand, the preparation method of the 3D printing ceramic slurry is characterized by comprising the following steps: adding the ceramic powder into an organic resin solution, and grinding to obtain 3D printing ceramic slurry; preferably, the time of the grinding treatment is 5 to 30 hours, preferably 10 to 25 hours.
Compared with the prior art, the Mg and Zn doped tricalcium phosphate material, the 3D printing ceramic slurry and the preparation method thereof have at least the following beneficial effects:
on one hand, the Mg and Zn doped tricalcium phosphate material provided by the embodiment of the invention can inhibit the generation of hydroxyapatite in the crystallization process by doping Mg and Zn elements in the tricalcium phosphate material, controlling the doping amount of the Mg element to be 10-15% and controlling the doping amount of the Zn element to be 5-10%, and can ensure that the Mg and Zn doped tricalcium phosphate material has better bioactivity under the synergistic action of the magnesium element and the zinc element, so that the Mg and Zn doped tricalcium phosphate material can be used for preparing bioceramics with better bioactivity, such as artificial bones and promoting the bone growth of human bodies.
Further, the particle size of the tricalcium phosphate material doped with Mg and Zn provided by the embodiment of the invention is 30-150nm, and the tricalcium phosphate material doped with Mg and Zn with the particle size is used as powder of the photocuring 3D printing ceramic slurry to finally print the bioceramic with good compactness.
According to the preparation method of the Mg and Zn doped tricalcium phosphate material provided by the embodiment of the invention, the reaction temperature of the preparation method is low, and no organic solvent is used in the preparation process; therefore, the preparation method of the Mg and Zn doped tricalcium phosphate material has the advantages of low energy consumption, low cost and no pollution. And the Mg and Zn doped tricalcium phosphate material with the grain diameter of 30-150nm can be prepared by controlling the reaction conditions.
On the other hand, according to the 3D printing ceramic slurry and the preparation method thereof provided by the embodiment of the invention, the tricalcium phosphate material doped with Mg and Zn is used as ceramic powder for preparing the 3D printing ceramic slurry, so that the 3D printed biological ceramic has better biological activity and compactness.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a morphology chart of Mg and Zn doped tricalcium phosphate material prepared in example 1.
Fig. 2 is a morphology chart of Mg and Zn doped tricalcium phosphate material prepared in example 2.
FIG. 3 is an XRD pattern of nano-tricalcium phosphate doped with different Mg and Zn contents; wherein, the curve (a) in fig. 3 is the XRD pattern of the Mg and Zn doped tricalcium phosphate material prepared in example 1; (b) the curve is the XRD pattern of the Mg and Zn doped tricalcium phosphate material prepared in example 2; (c) the curve is the XRD pattern of the Mg and Zn doped tricalcium phosphate material prepared in example 3; (d) the plot is the XRD pattern of Mg and Zn doped tricalcium phosphate material prepared in example 4.
FIG. 4 is an infrared spectrum of nanometer tricalcium phosphate doped with different Mg and Zn contents; wherein, the curve (a) in fig. 4 is an infrared spectrum of the Mg and Zn doped tricalcium phosphate material prepared in example 1; (b) the curve is the infrared spectrum of the Mg and Zn doped tricalcium phosphate material prepared in the example 2; (c) the curve is the infrared spectrum of the Mg and Zn doped tricalcium phosphate material prepared in example 3; (d) the curve is an infrared spectrum of the Mg and Zn doped tricalcium phosphate material prepared in example 4.
FIG. 5 shows the surface cell adhesion morphology (see a diagram in FIG. 5) and the surface EDS energy spectrum (see b diagram in FIG. 5) of Mg-Zn tricalcium phosphate coating prepared on the surface of titanium alloy (Ti-6Al-4V) by using the plasma spraying technology.
Fig. 6 is a topography of a ceramic after 3D printing and sintering by using the Mg and Zn doped tricalcium phosphate material prepared in example 1 as a ceramic powder to prepare a photocuring 3D printing ceramic slurry (solid content is 50%); wherein, the graph a in FIG. 6 is the shape of the bracket with a curved surface structure; FIG. 6 b is a cross-sectional view of the scanning electron microscope observation support; the c diagram in fig. 6 is a local enlarged topographic map of the area inside the dashed box in the b diagram.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In the prior art, the ceramic powder in the ceramic slurry for photocuring 3D printing is traditional calcium phosphate, alumina, zirconia and other materials, and the particle size of the ceramic powder is submicron (0.7-1.5 μm); the biological ceramic printed by 3D printing has the technical problems of low biological activity and low compactness.
Therefore, the inventor of the present invention prepares a doped tricalcium phosphate material as a ceramic powder in a photocuring 3D printing ceramic slurry to improve the biological activity of the printed bioceramic, and further adjusts the particle size of the prepared tricalcium phosphate material by the preparation method to improve the compactness of the printed bioceramic.
Further, the prior art has also been much investigated for doped tricalcium phosphate materials. However, the inventors of the present invention have found that the following problems exist in the conventional studies: on one hand, the doped metal ions and the calcium ions cannot sufficiently generate synergistic action, so that the biological activity cannot be effectively improved; on the other hand, the preparation method of the element-doped nano tricalcium phosphate at present mainly comprises a calcination method, a bionic solution preparation method, a mechanical stirring method and a flame spraying method. However, the above method mostly uses high temperature heating or organic solvents, etc., which increases the cost of preparing nano tricalcium phosphate and consumes more energy, which is not favorable for large-scale production and application.
In order to overcome the above mentioned technical problems, embodiments of the present invention provide a Mg and Zn doped tricalcium phosphate material, a 3D printing ceramic slurry and a preparation method thereof, specifically including:
in one aspect, an embodiment of the present invention provides a Mg and Zn doped tricalcium phosphate material, where in the Mg and Zn doped tricalcium phosphate material: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. The sum of the mole numbers of Mg and Zn is n3(ii) a Wherein n is1/n310-15% (i.e., the amount of Mg incorporated or the molar percentage of Mg incorporated); n is2/n3From 5 to 10% (i.e., the amount of Zn to be incorporated or the percentage molar ratio of Zn to be incorporated).
The invention not only can inhibit the generation of hydroxyapatite in the crystallization process by doping the magnesium element and the zinc element into the tricalcium phosphate, but also can inhibit the generation of the hydroxyapatite by controlling the Mg doping amount to be 10-15% and the Zn doping amount to be 5-10%, and the key point is that the tricalcium phosphate material doped with the Mg and the Zn has better bioactivity under the synergistic action of the magnesium element and the zinc element, so that the tricalcium phosphate material doped with the Mg and the Zn can be used for preparing the bioceramic with better bioactivity, such as artificial bone, and can promote the growth of bone substances of a human body.
Preferably, the particle size of the Mg and Zn-doped tricalcium phosphate material provided by the embodiment of the invention is 30-150nm, and the Mg and Zn-doped tricalcium phosphate material with the particle size is used as powder of the photocuring 3D printing ceramic slurry, so that the compactness of the bioceramic printed by 3D printing can be improved finally.
On the other hand, regarding the above-mentioned Mg and Zn doped tricalcium phosphate material, in order to reduce preparation energy consumption, reduce preparation cost, and avoid the use of organic solvents, the embodiment of the present invention designs the following preparation scheme:
preparing a first solution: dissolving calcium nitrate, magnesium nitrate and zinc nitrate in deionized water to form a first solution; preferably, in the first solution: the concentration of the calcium nitrate solution is 100-200g/L, the concentration of the magnesium nitrate solution is 10-40g/L, and the concentration of the zinc nitrate solution is 10-30 g/L. In the first solution: ca. The mol percentages of Mg and Zn respectively satisfy that Mg/(Ca + Mg + Zn) is 10-15%; 5-10% of Zn/(Ca + Mg + Zn).
Preparing a second solution: dissolving diammonium phosphate in deionized water, and then adjusting the pH value of the solution to 8.5-9.5 by using 25 wt% of ammonia water solution to obtain a second solution; preferably, the concentration of the diammonium hydrogen phosphate solution in the second solution is 25-100g/L, the volume of the second solution is equal to that of the first solution, and the molar quantity of phosphorus satisfies the following conditions: (Ca + Mg + Zn)/P is 1.5.
Mixing and reacting: and (2) quickly adding the first solution into the second solution, fully stirring, heating and preserving heat for several hours (reacting for a set time at a set temperature), carrying out suction filtration and cleaning (respectively cleaning with deionized water and alcohol for three times), and freeze-drying or drying to obtain the Mg and Zn doped tricalcium phosphate material (namely the Mg-Zn element-containing nano beta-TCP material). Preferably, the set temperature is 80-160 ℃, preferably 80-150 ℃; the reaction time is 6-24 h; the particle size of the prepared Mg and Zn doped tricalcium phosphate material can be controlled by controlling the reaction temperature and the reaction time.
From the above preparation process, it can be seen that: the preparation method provided by the embodiment of the invention has the advantages of low reaction temperature and no use of organic solvent, thus having low energy consumption, low cost and no pollution.
In yet another aspect, embodiments of the present invention provide a 3D printing ceramic paste (i.e., a photocuring 3D printing ceramic paste). The 3D printing ceramic slurry comprises ceramic powder (the ceramic powder is the above-mentioned Mg and Zn doped tricalcium phosphate material) and an organic resin solution; wherein, the volume fraction of the ceramic powder is 30-50%, and the volume fraction of the organic resin is 50-70%. The organic resin solution includes: 92-98.7 percent of light-cured resin by volume fraction, 0.1-1 percent of photoinitiator by volume fraction, 0.1-1 percent of flatting agent by volume fraction, 0.1-1 percent of defoaming agent by volume fraction and 1-5 percent of dispersant by volume fraction.
In addition, the preparation method of the 3D printing ceramic slurry comprises the following steps: adding the ceramic powder into an organic resin solution, and grinding to obtain 3D printing ceramic slurry; preferably, the time of the grinding treatment is 5 to 30 hours, preferably 10 to 25 hours.
The following are further detailed by specific experimental examples as follows:
the following experimental examples used the main raw materials: ca (NO)3)2(analytically pure), Mg (NO)3)2(analytically pure), Zn (NO)3)2(analytical grade), (NH4)2HPO4(analytically pure) and NH3·H2O (analytically pure).
Example 1
In this embodiment, a tricalcium phosphate material (β -TCP material) doped with Mg and Zn is prepared, which includes the following specific steps:
191.1g of Ca (NO) were weighed out3)2·4H2O, 24.4g Mg (NO)3)2·6H2O and 14.2g Zn (NO)3)2·6H2Dissolving O in 1L of deionized water, and uniformly stirring to obtain a first solution.
83.8g of (NH) are weighed4)2HPO4Dissolving the mixture in 1L of deionized water, stirring uniformly, dropwise adding ammonia water with the mass fraction of 25 wt% into the mixture, and adjusting the pH value to 9.5 to obtain a second solution.
And quickly adding the prepared first solution into the second solution. The first solution and the second solution were reacted at a temperature of 160 ℃ for 6 hours under magnetic stirring at a rotation speed of 300rpm, to obtain a reaction product.
After the reaction is finished, the reaction product is filtered and cleaned for three times by deionized water and alcohol respectively, and then is put into a drying oven to be dried for 12 hours at the temperature of 120 ℃, and finally the tricalcium phosphate material (beta-TCP material) doped with Mg and Zn is obtained. Wherein the Mg incorporation (Mg/(Ca + Mg + Zn) molar ratio) was 10%, and the Zn incorporation (Zn/(Ca + Mg + Zn) molar ratio) was 5%.
The morphology of the Mg and Zn doped tricalcium phosphate material prepared in this example is shown in fig. 1, the XRD pattern is shown in fig. 3a, and the infrared pattern is shown in fig. 4 a.
Example 2
In this embodiment, a tricalcium phosphate material (β -TCP material) doped with Mg and Zn is prepared, which includes the following specific steps:
191.1g of Ca (NO) were weighed out3)2·4H2O, 24.4g Mg (NO)3)2·6H2O and 14.2g Zn (NO)3)2·6H2Dissolving O in 1L of deionized water, and uniformly stirring to obtain a first solution.
83.8g of (NH) are weighed4)2HPO4Dissolving the mixture in 1L of deionized water, stirring uniformly, dropwise adding ammonia water with the mass fraction of 25 wt% into the mixture, and adjusting the pH value to 9.5 to obtain a second solution.
And quickly adding the prepared first solution into the second solution. The first solution and the second solution were reacted at a temperature of 80 ℃ for 24 hours under magnetic stirring at a rotation speed of 300rpm, to obtain a reaction product.
After the reaction is finished, the reaction product is filtered and cleaned for three times by deionized water and alcohol respectively, and then is put into a drying oven to be dried for 12 hours at the temperature of 120 ℃, and finally the tricalcium phosphate material (beta-TCP material) doped with Mg and Zn is obtained. Wherein the Mg incorporation (Mg/(Ca + Mg + Zn) molar ratio) was 10%, and the Zn incorporation (Zn/(Ca + Mg + Zn) molar ratio) was 5%.
The particle size of the Mg and Zn doped tricalcium phosphate material prepared by the embodiment is 30-50 nm; the morphology of the Mg and Zn doped tricalcium phosphate material prepared in this example is shown in fig. 2, the XRD pattern is shown in fig. 3b, and the infrared pattern is shown in fig. 4 b.
Example 3
In this embodiment, a tricalcium phosphate material (β -TCP material) doped with Mg and Zn is prepared, which includes the following specific steps:
167.9g of Ca (NO) are weighed3)2·4H2O, 36.4g Mg (NO)3)2·6H2O and 28.2g Zn (NO)3)2·6H2Dissolving O in 1L of deionized water, and uniformly stirring to obtain a first solution.
83.5g of (NH) are weighed4)2HPO4Dissolving the mixture in 1L of deionized water, stirring uniformly, dropwise adding ammonia water with the mass fraction of 25 wt% into the mixture, and adjusting the pH value to 9.5 to obtain a second solution.
And quickly adding the prepared first solution into the second solution. The first solution and the second solution were reacted at a temperature of 160 ℃ for 6 hours under magnetic stirring at a rotation speed of 300rpm, to obtain a reaction product.
After the reaction is finished, the reaction product is filtered and cleaned for three times by deionized water and alcohol respectively, and then is put into a drying oven to be dried for 12 hours at the temperature of 120 ℃, and finally the tricalcium phosphate material (beta-TCP material) doped with Mg and Zn is obtained. Wherein the Mg incorporation (Mg/(Ca + Mg + Zn) molar ratio) was 15%, and the Zn incorporation (Zn/(Ca + Mg + Zn) molar ratio) was 10%.
The XRD pattern and the ir pattern of the Mg and Zn doped tricalcium phosphate material prepared in this example are shown in fig. 3c and fig. 4c, respectively.
Example 4
In this embodiment, a tricalcium phosphate material (β -TCP material) doped with Mg and Zn is prepared, which includes the following specific steps:
167.9g of Ca (NO) are weighed3)2·4H2O, 36.4g Mg (NO)3)2·6H2O and 28.2g Zn (NO)3)2·6H2Dissolving O in 1L of deionized water, and uniformly stirring to obtain a first solution.
83.5g of (NH) are weighed4)2HPO4Dissolving the mixture in 1L of deionized water, stirring uniformly, dropwise adding ammonia water with the mass fraction of 25 wt% into the mixture, and adjusting the pH value to 9.5 to obtain a second solution.
And quickly adding the prepared first solution into the second solution. The first solution and the second solution were reacted at a temperature of 80 ℃ for 24 hours under magnetic stirring at a rotation speed of 300rpm, to obtain a reaction product.
After the reaction is finished, the reaction product is filtered and cleaned for three times by deionized water and alcohol respectively, and then is put into a drying oven to be dried for 12 hours at the temperature of 120 ℃, and finally the tricalcium phosphate material (beta-TCP material) doped with Mg and Zn is obtained. Wherein the Mg incorporation (Mg/(Ca + Mg + Zn) molar ratio) was 15%, and the Zn incorporation (Zn/(Ca + Mg + Zn) molar ratio) was 10%.
The XRD pattern and the ir pattern of the Mg and Zn doped tricalcium phosphate material prepared in this example are shown in fig. 3d and fig. 4d, respectively.
The tricalcium phosphate material doped with Mg and Zn prepared in this example was sprayed on the titanium alloy Ti6Al4V by plasma spraying, i.e., a beta-TCP coating with 15% Mg doping (Mg/(Ca + Mg + Zn) molar ratio) and 10% Zn doping (Zn/(Ca + Mg + Zn) molar ratio) was prepared on the surface of the titanium alloy Ti6Al 4V. Then, cell culture is performed on the coated surface. As can be seen from fig. 5: the cells spread well on the surface of the calcium phosphate material containing Mg and Zn, and the tail foot of the calcium phosphate material stretches obviously, so that the Mg and Zn doped tricalcium phosphate material prepared by the invention has good bioactivity.
Example 5
In this example, a photocurable tricalcium phosphate ceramic slurry for 3D printing (solid content: 50%) is prepared through the following specific steps:
12g of the Mg and Zn doped tricalcium phosphate material powder prepared in the example 1 (the powder density is 3 g/cm)3Volume of 4cm3) Adding the mixture into an organic resin solution; the organic resin solution was a 4mL mixture of 3.68mL of a photosensitive resin (1.45mL of HDDA, 1.20mL of G1122, 1.03mL of PEG400), 0.04mL of a photoinitiator (TPO-L), 0.04mL of a leveling agent (BYK 333), 0.04mL of an antifoaming agent (BYK 052N), and 0.2mL of a dispersant (BYK 111). Wherein the volume ratio of the Mg and Zn doped tricalcium phosphate material powder to the organic resin solution is 1: 1. After fully grinding for 24 hours, nano tricalcium phosphate ceramic slurry with solid content of 50 percent is prepared. The green nano-tricalcium phosphate blank printed by the nano-tricalcium phosphate ceramic slurry in a 3D mode is shown in figure 6.
As is apparent from fig. 1 and 4, the Mg and Zn doped tricalcium phosphate material prepared by the preparation method of Mg and Zn doped tricalcium phosphate material provided by the embodiment of the present invention has a particle size in the range of 30 to 150 nm. As can be seen from FIG. 5, the tricalcium phosphate material doped with Mg and Zn prepared by the embodiment of the invention has good bioactivity. In addition, as can be seen from fig. 6, when the Mg and Zn-doped tricalcium phosphate material prepared by the embodiment of the present invention is used as ceramic powder to prepare photocuring 3D printing ceramic slurry, the nano tricalcium phosphate ceramic printed by 3D has good compactness.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. An Mg and Zn doped tricalcium phosphate material, characterized in that in said Mg and Zn doped tricalcium phosphate material: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. Mole of Mg and ZnThe sum of the mole numbers is n3(ii) a Wherein n is1/n310-15%; n is2/n3Is 5-10%.
2. The Mg and Zn doped tricalcium phosphate material of claim 1, wherein said Mg and Zn doped tricalcium phosphate material has a particle size of 30-150 nm.
3. The process for preparing Mg and Zn doped tricalcium phosphate material according to claim 1 or 2, characterized in that it comprises the following steps:
1) reacting a first solution containing magnesium ions, zinc ions and calcium ions with a second solution containing phosphate ions at a set temperature for a set time to obtain a reaction product;
wherein in the first solution: the mole number of Mg element is n1(ii) a The mole number of Zn element is n2(ii) a Ca. The sum of the mole numbers of Mg and Zn is n3(ii) a Wherein n is1/n310-15%; n is2/n35-10%;
2) and after cleaning the reaction product, carrying out freeze-drying or drying treatment to obtain the Mg and Zn doped tricalcium phosphate material.
4. The process for the preparation of Mg and Zn doped tricalcium phosphate material according to claim 3, wherein in said step 1):
setting the time to be 6-24 h; and/or
The set temperature is 80-160 ℃.
5. The process for the preparation of Mg and Zn doped tricalcium phosphate material according to claim 3 or 4, characterized in that in said step 1):
the first solution is a mixed solution of calcium salt, magnesium salt and zinc salt;
preferably, the first solution is a mixed solution of calcium nitrate, magnesium nitrate and zinc nitrate;
further preferably, in the first solution: the concentration of calcium nitrate is 100-200g/L, the concentration of magnesium nitrate is 10-40g/L, and the concentration of zinc nitrate is 10-30 g/L.
6. The process for the preparation of Mg and Zn doped tricalcium phosphate material according to any one of claims 3 to 5, characterized in that in said step 1):
the second solution is ammonium dihydrogen phosphate solution with the pH value adjusted by ammonia water;
preferably, the concentration of the ammonium dihydrogen phosphate is 25-100 g/L;
preferably, the pH value of the second solution is 8.5-9.5;
preferably, the mass fraction of the ammonia water is 20 to 30 wt%, preferably 25 wt%.
7. The process for the preparation of Mg and Zn doped tricalcium phosphate material according to any one of claims 3 to 6, characterized in that in said step 1):
the volume ratio of the first solution to the second solution (1: 1.2) - (1.2: 1), preferably (1: 1.1) - (1.1: 1), and more preferably 1: 1; and/or
In the second solution, the mole number of the phosphorus element is n4(ii) a Wherein n is3/n4Is 1.45-1.65, preferably 1.5.
8. The process for the preparation of Mg and Zn doped tricalcium phosphate material according to any one of claims 1 to 7, wherein said step 1) is in particular: adding the first solution into the second solution, and reacting the first solution and the second solution at a set temperature for a set time under the condition of stirring.
9. 3D printing ceramic slurry, wherein the ceramic powder in the 3D printing ceramic slurry is the Mg and Zn doped tricalcium phosphate material of claim 1 or 2;
preferably, the 3D printing ceramic slurry comprises ceramic powder and an organic resin solution; wherein the volume fraction of the ceramic powder is 30-60%, and the volume fraction of the organic resin is 40-70%;
preferably, the organic resin solution includes: 92-98.7 percent of light-cured resin by volume fraction, 0.1-1 percent of photoinitiator by volume fraction, 0.1-1 percent of flatting agent by volume fraction, 0.1-1 percent of defoaming agent by volume fraction and 1-5 percent of dispersant by volume fraction.
10. The method for preparing the ceramic slurry for 3D printing according to claim 9, comprising the steps of:
adding the ceramic powder into an organic resin solution, and grinding to obtain 3D printing ceramic slurry;
preferably, the time of the grinding treatment is 5 to 30 hours, preferably 10 to 25 hours.
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US6090732A (en) * 1997-11-27 2000-07-18 Japan As Represented By Director General Of Agency Of Industrial Science And Technology Zinc-doped tricalcium phosphate ceramic material
CN1772603A (en) * 2005-09-28 2006-05-17 浙江大学 Prepn process of nanometer tricalcium phosphate powder with slowly released metal ion
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects

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US6090732A (en) * 1997-11-27 2000-07-18 Japan As Represented By Director General Of Agency Of Industrial Science And Technology Zinc-doped tricalcium phosphate ceramic material
CN1772603A (en) * 2005-09-28 2006-05-17 浙江大学 Prepn process of nanometer tricalcium phosphate powder with slowly released metal ion
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects

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CN113274545A (en) * 2021-04-26 2021-08-20 中国科学院上海硅酸盐研究所 Manganese-doped calcium silicate porous ceramic support and preparation method and application thereof

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