CN110054505B - Preparation method of nano-loaded zinc hydroxyapatite porous bioceramic - Google Patents
Preparation method of nano-loaded zinc hydroxyapatite porous bioceramic Download PDFInfo
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Abstract
The invention discloses a preparation method of nano-zinc-loaded hydroxyapatite porous bioceramic, and belongs to the technical field of preparation of biomedical materials. The method comprises the steps of weighing 99-97% of nano-hydroxyapatite and 1-7% of nano-zinc powder according to the mass ratio, carrying out ball milling to obtain composite powder, mixing the composite powder with a pore-forming agent ammonium bicarbonate, uniformly mixing, pressing to obtain a blank, and preparing the nano-zinc loaded hydroxyapatite porous bioceramic by using a spark plasma sintering technology. The porous biological ceramic prepared by the invention has uniform and pure components, controllable porosity of the material between 40 and 70 percent, compressive strength between 82 and 162Mpa and pore size between 50 and 600 mu m; the addition of zinc obviously improves the osteogenesis induction capability of the porous bioceramic, and the degradation rate is matched with the osteogenesis rate; is suitable for bone scaffolds, filling and repairing materials.
Description
Technical Field
The invention relates to a preparation method of nano-loaded zinc hydroxyapatite porous bioceramic, and belongs to the technical field of preparation of biomedical materials.
Background
In recent years, with the rapid development of national economy, the improvement of the living standard of people, the increasing aging of population and the remarkable improvement of the medical health level, more and more orthopedic patients are caused by industrial injury, traffic accidents, bone tumors, bone tuberculosis and other diseases. The bone materials currently used clinically are mainly autogenous bone and allogeneic bone. Autologous bone is the most ideal bone material, but the autologous bone has the problems of insufficient sources, complications of the bone supply area (such as infection, skin necrosis and permanent defect of the bone supply area) and the like; although allogeneic bone is the clinically preferred bone material in some cases, it has problems of graft rejection, disease transmission, long fusion time and the like. Therefore, research and development of artificial bone materials are urgently needed to solve the problems in clinical application of autogenous bone and allogeneic bone.
At present, the artificial bone material products which have acquired medical instrument registration certificates and are clinically applied mainly comprise: porous bioceramic for filling beamett bone (beta-tricalcium phosphate), Ceravital bioactive glass ceramic (CaO-Na 2O-SiO 2-P2O 5), Bongold artificial bone repair material (hydroxyapatite and type I Collagen), XC Collagen periosteum (alpha-tricalcium phosphate), Steobaone orthopedic repair material (hydroxyapatite/tricalcium phosphate and bone pleomorphin), Ruifu nanocrystalline Collagen-based bone repair material (nanocrystalline Collagen and phosphate), BAM bone-induced artificial bone (calcium phosphate), Naikang medical nano hydroxyapatite/polyamide 66 composite bone filling material (nano hydroxyapatite and polyamide 66) and the like. The problems of delayed healing or nonhealing of the implanted bone, mismatched degradation and osteogenesis rate of the artificial bone, broken deformation of the implanted bone material, high bone loss caused by collapse after the bone implantation, infection after the bone implantation, long-term sinus formation, long-term pain of the implanted bone part and the like still exist.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nano-zinc-loaded hydroxyapatite porous bioceramic; the nanometer zinc with the effect of promoting osteogenesis is loaded on the hydroxyapatite, and the preparation method by utilizing spark plasma sintering has the advantages of high temperature rise speed, short sintering time, low sintering temperature, clean preparation process and the like; the obtained porous bioceramic has pure components, controllable porosity and good osteogenesis induction capability, meets the performance requirements of clinical artificial bone materials for regeneration or reconstruction of hard tissues of organisms, and realizes clinical application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
(1) ball-milling and uniformly mixing nano zinc and nano hydroxyapatite powder, and drying to obtain nano zinc-loaded hydroxyapatite composite powder, wherein the mass percent of nano zinc in the composite powder is 1-7%, and the mass percent of nano hydroxyapatite in the composite powder is 99-93%;
(2) uniformly mixing the nano-zinc-loaded hydroxyapatite composite powder obtained in the step (1) with a pore-forming agent ammonium bicarbonate powder to obtain a mixed powder, wherein the mass percent of the composite powder in the mixed powder is 50-75%, and the mass percent of the ammonium bicarbonate powder is 50-25%;
(3) uniformly coating medical vaseline on the inner surface of the stainless steel mold, putting the mixed powder obtained in the step (3) into the mold, and pressing into a cylindrical blank;
(4) and (3) putting the cylindrical blank obtained in the step (3) into a graphite mold, putting the graphite mold into a discharge plasma sintering furnace for sintering, vacuumizing the system for 2-6 Pa, continuously filling argon with the purity of 99.999% and the flow rate of 60-80 ml/min for protective sintering, heating the system from room temperature to 100-150 ℃ at the heating rate of 100 ℃/min, preserving heat for 1-2 min, heating the system to 700 ℃ at the heating rate of 50 ℃/min, heating the system to 750-850 ℃ at the heating rate of 25 ℃/min, preserving heat for 5-10 min, cooling the system to room temperature after sintering, and demolding to obtain the nano-zinc-loaded hydroxyapatite porous bioceramic.
Preferably, the purity of the nano zinc is more than or equal to 99.9%, the particle size of the nano zinc is 50-60 nm, the purity of the nano hydroxyapatite powder is more than or equal to 99.7%, and the particle size of the nano hydroxyapatite powder is 80-100 nm.
Preferably, the ball milling conditions in step (1) of the present invention are: putting nano zinc and nano hydroxyapatite powder raw materials into a vacuum ball milling tank, adding stainless steel grinding balls, absolute ethyl alcohol and dispersant polyethylene glycol (the purity is analytically pure, the molecular weight is 400, and the addition amount is 0.5% of the mass of the powder), vacuumizing to 10-20 Pa, filling argon with the purity of 99.999%, placing the powder on a planetary ball mill, and ball milling for 6-8 hours at the rotating speed of 200-300 r/min; the mass ratio of balls to materials of the stainless steel grinding balls is 3: 1-3: 2, and the mass ratio of big balls to small balls is 1: 5-2: 5.
Preferably, the drying conditions in step (1) of the present invention are: and (4) drying in a vacuum drying oven at the drying temperature of 40-60 ℃.
Preferably, the purity of the ammonium bicarbonate powder in the step (2) of the invention is analytical purity, and the average particle size is 100-500 μm.
Preferably, the pressure applied in step (3) of the invention is 25-30 KN.
The invention has the beneficial effects that:
(1) the material selected by the method has pure components, and the selected ammonium bicarbonate can be completely volatilized at a lower sintering temperature without any residue; the adoption of the spark plasma sintering technology can reduce the sintering temperature, avoid the loss of zinc element caused by overhigh temperature, reduce the heat preservation time and avoid the decomposition of hydroxyapatite caused by overlong calcination time.
(2) The material can obtain biological ceramics with different porosities and different strengths by adjusting the proportion of the composite powder and the pore-forming agent according to different requirements, and can be used as a bone scaffold, a filling material and a repairing material; the porosity of the porous material is 40-70%, the pore size is 20-500 mu m, the pores and the pores coexist, and the unique pore structure and the rough inner and outer surfaces are favorable for adhesion and proliferation of osteoblasts, promote the growth of bone tissues and improve the bone forming activity of the material.
(3) Has good osteogenesis inducing capacity; the degradable active nano metal zinc with the effect of promoting osteogenesis is loaded on the porous hydroxyapatite, so that the material not only can improve the osteogenesis induction capability of the bioceramic, but also has certain antibacterial property; can meet the clinical performance requirements of the artificial bone material for regeneration or reconstruction of hard tissues of organisms and realize the clinical application of the artificial bone material.
Drawings
Fig. 1X-ray diffraction pattern of nano zinc-loaded hydroxyapatite porous bioceramic prepared in example 4 of the present invention;
FIG. 2 shows the surface morphology of the nano-zinc-loaded hydroxyapatite porous bioceramic prepared in example 4;
FIG. 3 is a mineralized morphology of the nano-loaded zinc hydroxyapatite porous bioceramic prepared in example 4;
fig. 4 degradation performance of the nano-zinc-loaded hydroxyapatite porous bioceramic prepared in example 4;
fig. 5 the zinc ion releasing performance of the nano-zinc-hydroxyapatite-loaded porous bioceramic prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1
(1) The method comprises the steps of taking nano zinc with the purity of more than or equal to 99.9% and the particle size of 50-60 nm and nano hydroxyapatite powder with the purity of more than or equal to 99.7% and the particle size of 80-100 nm as raw materials, and respectively weighing the nano zinc and the nano hydroxyapatite powder according to the mass ratio of 1: 99.
(2) Putting the powder raw materials weighed in the step (1) into a vacuum ball milling tank, adding stainless steel grinding balls, absolute ethyl alcohol and dispersant polyethylene glycol, vacuumizing to 10Pa, then filling argon with the purity of 99.999%, putting the mixture on a planetary ball mill, ball milling for 8 hours at the rotating speed of 300r/min, and drying and grinding the mixture in a vacuum drying oven at the temperature of 60 ℃ to obtain the nano zinc-loaded hydroxyapatite composite powder.
(3) And (3) uniformly mixing the nano-zinc-loaded hydroxyapatite composite powder obtained in the step (2) with a pore-forming agent ammonium bicarbonate powder with the purity AR and the average particle size of 500 mu m according to a mass ratio of 75:25 to obtain mixed powder.
(4) And (4) putting the mixed powder obtained in the step (3) into a self-made stainless steel mold, applying 25KN of pressure, and carrying out cold isostatic pressing to obtain a cylindrical blank.
(5) And (3) putting the cylindrical blank obtained in the step (4) into a graphite mold, putting the graphite mold into a discharge plasma sintering furnace for sintering, vacuumizing the system by 2Pa, continuously filling argon with the purity of 99.999% and the flow rate of 60ml/min for protective sintering, heating from room temperature to 150 ℃ at the heating rate of 100 ℃/min, then preserving heat for 1min, heating to 700 ℃ at the heating rate of 50 ℃/min, finally heating to 750 ℃ at the heating rate of 25 ℃/min, preserving heat for 5min, cooling to room temperature along with the furnace after sintering is finished, and demolding to obtain the nano-zinc-loaded hydroxyapatite porous bioceramic.
Example 2
The preparation method comprises the steps of taking nano zinc with the purity of more than or equal to 99.9 percent and the particle size of 50-60 nm and nano hydroxyapatite powder with the purity of more than or equal to 99.7 percent and the particle size of 80-100 nm as raw materials, respectively weighing the nano zinc and the nano hydroxyapatite powder according to the mass ratio of 3:97, and keeping the other process steps and parameters consistent with those of example 1.
Example 3
The preparation method comprises the steps of taking nano zinc with the purity of more than or equal to 99.9 percent and the particle size of 50-60 nm and nano hydroxyapatite powder with the purity of more than or equal to 99.7 percent and the particle size of 80-100 nm as raw materials, respectively weighing the nano zinc and the nano hydroxyapatite powder according to the mass ratio of 5:95, and keeping the other process steps and parameters consistent with those of example 1.
Example 4
The preparation method comprises the steps of taking nano zinc with the purity of more than or equal to 99.9 percent and the particle size of 50-60 nm and nano hydroxyapatite powder with the purity of more than or equal to 99.7 percent and the particle size of 80-100 nm as raw materials, respectively weighing the nano zinc and the nano hydroxyapatite powder according to the mass ratio of 5:95, and keeping the other process steps and parameters consistent with those of example 1.
Performing X-ray diffractometer (XRD) analysis (as shown in figure 1) on the prepared nano-zinc-loaded hydroxyapatite porous bioceramic; as can be seen from the figure, the material takes HA as the main body, the peak position is not affected by the addition of Zn, the basic composition of the substance is not changed, and the main phase is still HA; no HA decomposition products CaO and beta-Ca are found in the map3(PO4)2Indicating that HA is not decomposed at 750 ℃; in addition, NH is not seen in XRD phase analysis4HCO3The ceramic has complete volatilization in the sintering process, and the prepared ceramic has definite components and ensured safety.
Measuring the porosity of the material by using a ceramic porosity analyzer; the compressive strength of the material was tested on a mechanical testing machine according to GB/T4740-; specific results are shown in table 1; the compressive strength of the material can meet the clinical requirement.
TABLE 1 porosity and compressive strength of porous bioceramics at different zinc contents
Analyzing the morphology of the prepared nano-zinc-loaded hydroxyapatite porous bioceramic by using a Scanning Electron Microscope (SEM) (as shown in figure 2); observing the pore morphology (as shown in figure 2), wherein the prepared materials have a large pore structure and a small pore structure which are mutually communicated, the pore diameter is 50-500 mu m, and the prepared materials are uniformly distributed; whether the bone scaffold material or the bone filling material is a bone scaffold material, the bone filling material HAs proper size and occupies certain volume fraction of pores (the porosity is generally expected to be more than 40%, macropores and micropores coexist, the pore diameter of the macropores is 100-300 mu m, and the pore diameter of the micropores is more than 10 mu m), so that a channel and a growth space can be provided for the growth of cells, fibrous tissues and bone tissues, the contact surface area of tissue fluid and HA is increased, the degree and the speed of bone growth are determined by influencing metabolism, nutrient transmission and blood vessel growth, and the bone repair process is accelerated; meanwhile, the specific surface area of the material is increased by the porous structure, and Zn can be increased2+The local release concentration can accelerate the growth of new bone and enhance the capability of bone formation.
Soaking the nano-zinc-loaded hydroxyapatite porous bioceramic in an SBF solution, placing the SBF solution in a constant-temperature water bath box at 37 ℃, testing the degradation performance of the material (as shown in figure 3), and finding that the degradation rate of the material is always accelerated; zn of the porous bioceramic loaded with nano zinc hydroxyapatite by combining the zinc ion release performance (as shown in figure 4)2+The release increases gradually with the soaking time from Zn2+As can be seen on the graph, the 1d Zn2+The release speed is the fastest, and gradually becomes gentle along with the increase of the soaking time until the 7d still has Zn2+Release into simulated body fluid, indicating Zn2+In a slow, sustained manner. Nano-zinc-loaded hydroxyapatite porous bioceramic and in-vitro slow and sustainable Zn2+The release characteristics are related to the porous structure of the material.
The antibacterial rate of the bioceramic with 1% of zinc content is 83.18%, the antibacterial rate of the bioceramic with 3% of zinc content is 91.30%, the antibacterial rate of the bioceramic with 5% of zinc content is 97.68%, and the antibacterial rate of the bioceramic with 7% of zinc content is as high as 99.13%; the antibacterial rate of the material is gradually increased along with the increase of the zinc content.
The nano-zinc-loaded hydroxyapatite porous bioceramic prepared in other examples has similar properties through the same analysis method.
Example 5
(1) The method comprises the steps of taking nano zinc with the purity of more than or equal to 99.9% and the particle size of 50-60 nm and nano hydroxyapatite powder with the purity of more than or equal to 99.7% and the particle size of 80-100 nm as raw materials, and weighing the nano zinc and the nano hydroxyapatite powder according to the mass ratio of 7: 93.
(2) Putting the powder raw materials weighed in the step (1) into a vacuum ball milling tank, adding stainless steel grinding balls, absolute ethyl alcohol and dispersant polyethylene glycol, vacuumizing to 10Pa, then filling argon with the purity of 99.999%, putting the mixture on a planetary ball mill, ball milling for 8 hours at the rotating speed of 300r/min, and drying and grinding the mixture in a vacuum drying oven at the temperature of 60 ℃ to obtain the nano zinc-loaded hydroxyapatite composite powder.
(3) And (3) uniformly mixing the nano-zinc-loaded hydroxyapatite composite powder obtained in the step (2) with a pore-forming agent ammonium bicarbonate powder with the purity AR and the average particle size of 500 mu m according to the mass ratio of 25:75 to obtain mixed powder.
(4) And (4) putting the mixed powder obtained in the step (3) into a self-made stainless steel mold, applying 25KN of pressure, and pressing into a cylindrical blank.
(5) And (3) putting the cylindrical blank obtained in the step (4) into a graphite mold, putting the graphite mold into a discharge plasma sintering furnace for sintering, vacuumizing the system by 2Pa, continuously filling argon with the purity of 99.999% and the flow rate of 80ml/min for protective sintering, heating the system from room temperature to 100 ℃ at the heating rate of 100 ℃/min, preserving the heat for 2min, then heating the system to 700 ℃ at the heating rate of 50 ℃/min, finally heating the system to 850 ℃ at the heating rate of 25 ℃/min, preserving the heat for 5min, cooling the system to room temperature along with the furnace after sintering is finished, and demolding to obtain the nano-zinc-loaded hydroxyapatite porous bioceramic.
Example 6
The nano zinc-loaded hydroxyapatite composite powder and a pore-forming agent ammonium bicarbonate powder with the purity AR and the average particle size of 500 mu m are uniformly mixed according to the mass ratio of 50:50 to obtain mixed powder, and other process steps and parameters are the same as those in the example 5.
The results show that the porosity and compressive strength of the porous bioceramic loaded with nano-zinc hydroxyapatite prepared in the embodiment examples 5 and 6 are shown in table 2, and the porosity of the material can be changed according to different purposes, so that different clinical requirements can be met.
TABLE 27 compressive strength of zinc porous bioceramics at different porosities
Claims (6)
1. A preparation method of a nano-zinc-loaded hydroxyapatite porous biological ceramic material is characterized by comprising the following steps:
(1) ball-milling and uniformly mixing nano zinc and nano hydroxyapatite powder, and drying to obtain nano zinc-loaded hydroxyapatite composite powder, wherein the mass percent of nano zinc in the composite powder is 1-7%, and the mass percent of nano hydroxyapatite in the composite powder is 99-93%;
(2) uniformly mixing the nano-zinc-loaded hydroxyapatite composite powder obtained in the step (1) with a pore-forming agent ammonium bicarbonate powder to obtain a mixed powder, wherein the mass percent of the composite powder in the mixed powder is 50-75%, and the mass percent of the ammonium bicarbonate powder is 50-25%;
(3) uniformly coating medical vaseline on the inner surface of the stainless steel mold, putting the mixed powder obtained in the step (3) into the mold, and pressing into a cylindrical blank;
(4) and (3) putting the cylindrical blank obtained in the step (3) into a graphite mold, putting the graphite mold into a discharge plasma sintering furnace for sintering, vacuumizing the system for 2-6 Pa, continuously filling argon with the purity of 99.999% and the flow rate of 60-80 mL/min for protective sintering, firstly heating to 100-150 ℃, then preserving heat for 1-2 min, then heating to the sintering temperature of 750-850 ℃, preserving heat for 5-10 min, cooling to room temperature along with the furnace after sintering is finished, and demolding to obtain the nano zinc-loaded hydroxyapatite porous bioceramic.
2. The preparation method of the nano-zinc-loaded hydroxyapatite porous bioceramic material according to claim 1, characterized by comprising the following steps: the purity of the nano zinc is more than or equal to 99.9%, the particle size is 50-60 nm, the purity of the nano hydroxyapatite powder is more than or equal to 99.7%, and the particle size is 80-100 nm.
3. The preparation method of the nano-zinc-loaded hydroxyapatite porous bioceramic material according to claim 1, characterized by comprising the following steps: the ball milling conditions in the step (1) are as follows: putting nano zinc and nano hydroxyapatite powder raw materials into a vacuum ball milling tank, adding stainless steel grinding balls, absolute ethyl alcohol and dispersant polyethylene glycol, vacuumizing to 10-20 Pa, then filling argon with the purity of 99.999%, placing on a planetary ball mill, and ball milling for 6-8 hours at the rotating speed of 200-300 r/min; the mass ratio of balls to materials of the stainless steel grinding balls is 3: 1-3: 2, and the mass ratio of big balls to small balls is 1: 5-2: 5.
4. The preparation method of the nano-zinc-loaded hydroxyapatite porous bioceramic material according to claim 1, characterized by comprising the following steps: the drying conditions in the step (1) are as follows: and (4) drying in a vacuum drying oven at the drying temperature of 40-60 ℃.
5. The preparation method of the nano-zinc-loaded hydroxyapatite porous bioceramic material according to claim 1, characterized by comprising the following steps: the purity of the ammonium bicarbonate powder in the step (2) is analytically pure, and the average particle size is 100-500 mu m.
6. The preparation method of the nano-zinc-loaded hydroxyapatite porous bioceramic material according to claim 1, characterized by comprising the following steps: the pressure applied in the step (3) is 25-30 k N.
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| CN112620630B (en) * | 2020-12-15 | 2023-09-26 | 昆明理工大学 | Preparation method of zinc-magnesium/hydroxyapatite porous composite material |
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