CN114163230A - Superfine uniform-grain calcium phosphate biological ceramic and preparation method thereof - Google Patents
Superfine uniform-grain calcium phosphate biological ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a calcium phosphate biological ceramic with superfine uniform grains and a preparation method thereof, belongs to the technical field of biomedical materials, and solves the problem of poor mechanical property of the calcium phosphate biological ceramic in the prior art. The preparation method of the calcium phosphate biological ceramic with ultrafine and uniform grains comprises the following steps: pre-sintering the calcium phosphate initial powder at low temperature to form a primary crystal phase; performing wet ball milling treatment on the pre-sintered calcium phosphate powder, performing gradient centrifugation on the ball-milled slurry, and separating to obtain the calcium phosphate powder with small grain size and narrow distribution; preparing the calcium phosphate powder obtained after ball milling and centrifugation into a ceramic green body; and (3) sintering the ceramic green body in two steps, and immediately quenching and rapidly cooling after the second-step sintering heat preservation is finished to obtain the calcium phosphate biological ceramic. The calcium phosphate ceramic prepared by the method has uniform grain size, excellent mechanical property and better bioactivity, and meets the requirement of clinical load-bearing bone defect repair.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a calcium phosphate biological ceramic with ultrafine uniform grains and a preparation method thereof.
Background
Calcium phosphate bioceramics are used in the field of bone repair because of their good biocompatibility, osteoinductive properties and osteogenic activity, but cannot be used in the field of load-bearing bone repair because of their natural brittleness and lower fracture toughness.
The prior art discloses that the mechanical property of calcium phosphate ceramic can be obviously improved by refining the grain size of calcium phosphate ceramic, for example, the literature (Applied Mechanics and Materials, 2011, 83: 237-. Therefore, how to improve the mechanical property of the calcium phosphate ceramic by optimizing the grain size of the calcium phosphate ceramic on the premise of not influencing the osteoinductive capacity of the calcium phosphate ceramic is of great significance.
In the prior art, the sintering process of calcium phosphate Ceramic is an important factor influencing the grain size of Ceramic, for example, two-step sintering can effectively inhibit abnormal growth of grains in the grain sintering process, and two-step sintering can be adopted to prepare nano calcium phosphate Ceramic (Journal of the European Ceramic Society, 2011, 31: 19-27). However, the calcium phosphate ceramics obtained by the method has limited effect on improving the mechanical property of the calcium phosphate ceramics.
Therefore, how to maintain the excellent osteoinductive activity of the calcium phosphate ceramic and simultaneously endow the calcium phosphate ceramic with good mechanical properties to meet the clinical requirements on the regeneration and repair material for load-bearing bone defects is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing a calcium phosphate bioceramic with ultra-fine uniform grains, which solves the problem of poor mechanical properties of calcium phosphate bioceramic in the prior art.
The second purpose of the invention is to provide the calcium phosphate bioceramic prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of calcium phosphate bioceramic with ultrafine and uniform grains, which comprises the following steps:
s1, low-temperature presintering: pre-sintering the calcium phosphate initial powder at a low temperature to form a primary crystal phase;
s2, ball milling and centrifuging: performing wet ball milling treatment on the pre-sintered calcium phosphate powder, performing gradient centrifugation on the ball-milled slurry, and separating to obtain the calcium phosphate powder with small grain size and narrow distribution;
s3, forming: preparing the calcium phosphate powder obtained by ball milling and centrifugal optimization into a ceramic green body;
s4, two-step sintering: and (3) sintering the ceramic green body in two steps, and immediately quenching and rapidly cooling after the second-step sintering heat preservation is finished to obtain the calcium phosphate biological ceramic.
The calcium phosphate initial powder comprises at least one of hydroxyapatite initial powder, tricalcium phosphate initial powder, biphasic calcium phosphate initial powder and biphasic calcium phosphate initial powder.
In some embodiments of the invention, in the step S1, the low-temperature pre-sintering temperature is 500-900 ℃, and the pre-sintering time is 2-8 h.
In some embodiments of the invention, in S2, the medium for wet ball milling is absolute ethyl alcohol or/and water, the rotation speed is 300-1500 rpm, and the ball milling time is 5-30 hours.
In some embodiments of the invention, the number of gradient centrifugations is 2 or more.
In some embodiments of the invention, three gradient centrifuges are used, with the centrifuge speeds being sequentially increased. Centrifuging the ball-milled slurry at 5000-6000 rpm, then centrifuging the supernatant for the second time at 8000-10000 rpm, centrifuging the supernatant obtained by the second centrifugation at 10000-12000 rpm, taking the precipitate, and drying to obtain the calcium phosphate powder with small grain size and narrow distribution.
Preferably, the time of each centrifugation is 3-10 min, and more preferably 5 min.
In some embodiments of the invention, the particle size of the calcium phosphate powder obtained by ball milling and centrifugal optimization is 50-100 nm.
In some embodiments of the invention, calcium phosphate powder obtained by ball milling and centrifugal optimization is dried, ground and sieved, and then is subjected to cold isostatic pressing to prepare a ceramic green body.
In some embodiments of the invention, in the step S4, the sintering temperature in the first step is 950-1150 ℃, and the heat preservation time is 0-30 min;
or/and the temperature of the second sintering step is 650-950 ℃, and the heat preservation time is 2-40 h.
In some embodiments of the present invention, in S4, the quenching rapid cooling process is an air quenching rapid cooling process.
The invention provides the calcium phosphate bioceramic prepared by the method.
In some embodiments of the invention, the calcium phosphate bioceramic crystal size is 200nm or less.
In some embodiments of the present invention, the calcium phosphate bioceramic has a compressive strength of 100 to 150 MPa.
Compared with the prior art, the invention has the following beneficial effects:
the invention has scientific design, simple method and simple and convenient operation. The calcium phosphate powder is pre-sintered to form a primary crystal phase, and then is subjected to wet ball milling to reduce the grain size of the calcium phosphate powder, and then is subjected to gradient centrifugation to obtain the calcium phosphate powder with small grain size and narrow distribution. The size of calcium phosphate crystal grains is controlled by two-step sintering, and the mechanical property of the calcium phosphate bioceramic is optimized by direct quenching and rapid cooling treatment after the two-step calcination.
The calcium phosphate ceramic prepared by the method has uniform grain size, excellent mechanical property and better bioactivity, and meets the requirement of clinical load-bearing bone defect repair.
Drawings
FIG. 1 is a microscopic morphology diagram of calcium phosphate powder; wherein A is a microstructure diagram of the calcium phosphate initial powder, and B is a microstructure diagram of the calcium phosphate powder in example 1; C. and D is a microscopic morphology graph of the calcium phosphate powder obtained in example 2 when the pre-sintering temperature is 700 ℃ and 900 ℃.
FIG. 2 is a diagram of conventional calcium phosphate ceramic grains, wherein A is a microscopic morphology diagram and B is a particle size distribution diagram;
FIG. 3 is a graph of the crystal grain of the ultrafine uniform-grained calcium phosphate bioceramic of example 1, wherein A is a microscopic morphology graph and B is a distribution graph of the grain size;
FIG. 4 is a graph of the ultrafine uniform grained calcium phosphate bioceramic of example 2, No. 3, wherein A is a microscopic morphology graph and B is a grain size distribution graph;
FIG. 5 is a graph of the mechanical properties of calcium phosphate ceramics.
FIG. 6 is an ALP activity diagram after 7 days of coculture of bioceramic and stem cells (BMSCs) in test example I.
FIG. 7 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
The calcium phosphate initial powder in the embodiment of the invention is prepared by a wet precipitation method, and the preparation method is shown in Journal of the American Ceramic Society, 2006: 2295-2297. The calcium phosphate initial powder can also be prepared by a template method, a sol-gel method and other methods, and meanwhile, the commercially available calcium phosphate ceramic powder can also be selected.
The drying in the embodiment of the invention is realized by adopting a conventional oven.
The preparation method of the traditional calcium phosphate ceramic in the embodiment of the invention comprises the following steps: taking hydroxyapatite initial powder, directly carrying out cold isostatic pressing to obtain a ceramic green body, carrying out one-step sintering, namely, keeping the temperature for 2 hours at the sintering temperature of 1100 ℃, and cooling along with a furnace after the heat preservation is finished to obtain the ceramic. The grain pattern is shown in figure 2, wherein A is a micro-topography pattern, and B is a particle size distribution pattern.
Example 1
The embodiment discloses a preparation method of calcium phosphate bioceramic with ultrafine uniform grains, which comprises the following steps:
(1) weighing 6g of hydroxyapatite initial powder (HA), and pre-sintering at 600 deg.C for 4h to obtain pre-sintered powder, wherein the microstructure of the initial powder is shown in figure 1A.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is absolute ethyl alcohol, the volume is 50mL, the ball milling rotation speed is 450rpm, and the ball milling time is 14 h; centrifuging the ball-milled slurry for 5min at 5000rpm, centrifuging the centrifuged supernatant for 5min at 10000rpm for the second time, centrifuging the supernatant obtained by the second centrifugation for 5min at 12000rpm, taking the precipitate, drying, grinding and screening to obtain the calcium phosphate powder with small grain size and narrow distribution. The microstructure of the calcium phosphate powder is shown in figure 1B.
(3) And (3) carrying out cold isostatic pressing on the calcium phosphate powder with small grain size and narrow distribution to obtain the ceramic green body.
(4) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 1150 ℃, the temperature is kept for 1min, the temperature of the second step is 950 ℃, the temperature is kept for 20h, the crucible is immediately taken out after the temperature is kept, air quenching and cooling are carried out, and the reinforced calcium phosphate ceramic is obtained, the microstructure of which is shown in a figure 3A, and the grain size distribution of grains is shown in a figure 3B.
The microstructure of the optimized calcium phosphate powder prepared in this example is shown in fig. 1B, and compared with the non-optimized calcium phosphate initial powder (shown in fig. 1A), the particle size is smaller and the distribution is narrower.
The microstructure of the reinforced calcium phosphate ceramic of this example is shown in fig. 3A, and compared with the conventional calcium phosphate ceramic (average grain size of 453.1 ± 231.5nm), the ceramic grains obtained in this example are greatly refined and uniformly distributed, and the average grain size is 150.0 ± 47.7 nm.
The mechanical properties of the reinforced calcium phosphate ceramic of this example are shown in fig. 5, and the compressive strength reaches 120.9 ± 12.9MPa compared with the conventional calcium phosphate ceramic (80.6 ± 5.9 MPa).
Example 2
In this example, whether or not the low-temperature pre-sintering is performed and the temperature of the low-temperature pre-sintering are examined: when the low-temperature presintering is not adopted, compared with the embodiment 1, the step (1) is not adopted, and the rest conditions are the same; when different pre-sintering temperatures are used, the pre-sintering temperatures are shown in the following table, and the rest conditions are the same as in example 1.
Table 1 pre-sintering temperature investigation result table
As can be seen from the above table, when the pre-sintering temperature is 600-900 ℃, the obtained calcium phosphate bioceramic has small average grain size, narrow distribution, good compressive strength and good compressive strength.
The micro-morphology of the calcium phosphate powder prepared at the pre-sintering temperature of 700 ℃ is shown in figure 1C, and compared with the calcium phosphate initial powder which is not optimized (shown in figure 1A), the calcium phosphate initial powder has finer particles and narrower distribution. The microstructure of the reinforced calcium phosphate ceramic prepared at the pre-sintering temperature of 700 ℃ is shown in figure 4A, and compared with the traditional calcium phosphate ceramic (the average grain size is 453.1 +/-231.5 nm), the ceramic grains are greatly refined and uniformly distributed, and the average grain size is 142.9 +/-53.9 nm; the mechanical property is shown in figure 5, and compared with the traditional calcium phosphate ceramic (80.6 +/-5.9 MPa), the compressive strength of the calcium phosphate ceramic reaches 110.9 +/-10.3 MPa.
The microstructure of the optimized calcium phosphate powder prepared at the pre-sintering temperature of 900 ℃ is shown in figure 1D, and compared with the non-optimized calcium phosphate initial powder, the particle size is smaller and the distribution is narrower.
When the sintering temperature of the pre-sintering is less than 600 ℃ or more than 900 ℃, the crystal grain of the prepared reinforced calcium phosphate is increased, and the compressive strength is reduced; therefore, the pre-sintering temperature is selected to be 600-900 ℃.
Example 3
In this example, whether to quench or not and different quenching methods are examined: when not quenching, in the two-step sintering, after the second-step sintering is finished and the heat preservation is finished, the second-step sintering is cooled along with the furnace, and the other conditions are the same as those of the embodiment 1; when different quenching modes are adopted, the specific quenching conditions are shown in the following table, and the rest conditions are the same as those in example 1:
table 2 quenching mode investigation result table
As can be seen from the above table, the quenching mode of the invention is superior to the graded quenching cooling and the non-quenching furnace cooling.
Example 4
This example examined whether gradient separation was employed and the number of times of gradient separation: when gradient separation is not adopted, removing the solvent from the slurry after wet ball milling, and drying, wherein the other conditions are the same as in example 1; when gradient separation is used, the gradient separation conditions are shown in the following table, and the rest of the conditions are the same as in example 1.
TABLE 4 gradient separation investigation results Table
As can be seen from the above table, the calcium phosphate powder with uniform particle size and narrow distribution range can be obtained by adopting a gradient centrifugation method after wet ball milling; and the distribution range of the calcium phosphate powder is narrow, which is more beneficial to improving the mechanical property of the calcium phosphate biological ceramic.
Example 5
(1) Weighing 6g of tricalcium phosphate initial powder (TCP), and carrying out low-temperature presintering on the TCP at the temperature of 600 ℃ for 8 hours.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is deionized water, the ball milling rotation speed is 300rpm, the ball milling time is 30 hours, performing gradient centrifugation on powder slurry after ball milling, dividing into three times of centrifugation, firstly performing aging filtration, taking supernate and performing 6000rpm, then respectively taking supernate and performing centrifugal separation at 8000rpm and 12000rpm, drying precipitates, then performing grinding and screening, and then performing die tabletting to obtain a ceramic green body.
(3) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 1050 ℃, keeping the temperature for 1min, the temperature of the second step is 650 ℃, keeping the temperature for 40h, immediately taking out the crucible after the heat preservation is finished, and carrying out air quenching to obtain the reinforced tricalcium phosphate ceramic.
Example 6
(1) 6g of biphasic calcium phosphate starting powder (HA: TCP ═ 5: 5) was weighed out and presintered at 900 ℃ for 2 h.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is deionized water, the ball milling rotation speed is 3000rpm, the ball milling time is 5 hours, performing gradient centrifugation on powder slurry after ball milling, dividing into three times of centrifugation, firstly performing aging filtration, taking supernate, performing 6000rpm, then respectively taking supernate, performing centrifugal separation at 8000rpm and 12000rpm, drying precipitates, then performing grinding and screening, and then performing die tabletting to obtain a ceramic green body.
(3) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 950 ℃, preserving heat for 30min, the temperature of the second step is 650 ℃, preserving heat for 40h, immediately taking out the crucible after heat preservation, and carrying out air quenching to obtain the reinforced tricalcium phosphate ceramic.
Example 7
(1) 6g of hydroxyapatite initial powder (HA) is weighed and presintered at a low temperature of 650 ℃ for 5 hours.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is deionized water, the ball milling rotation speed is 1000rpm, the ball milling time is 10 hours, performing gradient centrifugation on powder slurry after ball milling, dividing into three times of centrifugation, firstly performing aging filtration, taking supernate, performing 5000rpm centrifugation, then respectively taking supernate, performing 10000rpm centrifugation and 12000rpm centrifugation, drying precipitates, then performing grinding screening, and then performing 3D printing to obtain a ceramic green body.
(3) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 1100 ℃, keeping the temperature for 1min, the temperature of the second step is 850 ℃, keeping the temperature for 10h, immediately taking out the crucible after the heat preservation is finished, and carrying out air quenching to obtain the reinforced calcium phosphate ceramic.
Example 8
(1) 6g of biphasic calcium phosphate initial powder (HA: TCP ═ 5: 5) was weighed out and presintered at a low temperature of 800 ℃ for 4 h.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is absolute ethyl alcohol, the ball milling rotation speed is 2000rpm, the ball milling time is 10 hours, performing gradient centrifugation on powder slurry after ball milling, dividing into three times of centrifugation, firstly aging, filtering, taking supernate, performing centrifugal separation at 5000rpm, then taking supernate, performing centrifugal separation at 10000rpm and 12000rpm, drying precipitates, then performing grinding and screening, and then performing hydrogen peroxide foaming to obtain a ceramic green body.
(3) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 1050 ℃, keeping the temperature for 3min, the temperature of the second step is 950 ℃, keeping the temperature for 20h, immediately taking out the crucible after the heat preservation is finished, and carrying out air quenching to obtain the reinforced calcium phosphate ceramic.
Example 9
(1) 6g of hydroxyapatite initial powder (HA) is weighed and presintered at a low temperature of 800 ℃ for 4 hours.
(2) Performing wet ball milling on the pre-sintered powder, wherein the medium is a mixture (1: 1) of absolute ethyl alcohol and deionized water, the ball milling rotation speed is 1500rpm, the ball milling time is 5 hours, the ball-milled powder slurry is subjected to gradient centrifugation which is divided into three times of centrifugation, firstly, aging and filtering are performed, supernatant fluid is obtained and subjected to 5000rpm, then, the supernatant fluid is respectively obtained and subjected to 10000rpm and 12000rpm centrifugal separation, the precipitate is dried, then, grinding and screening are performed, and then, cold isostatic pressing is performed to obtain the ceramic green body.
(3) And (3) sintering the ceramic green body in two steps, wherein the temperature of the first step is 1100 ℃, keeping the temperature for 1min, the temperature of the second step is 900 ℃, keeping the temperature for 2h, immediately taking out the crucible after the heat preservation is finished, and carrying out air quenching to obtain the reinforced calcium phosphate ceramic.
Test example I materials promoting Stem cell osteogenesis Activity
1. Test subjects: bone marrow mesenchymal stem cells (BMSCs) were selected and provided by the cell bank of the China academy of sciences (Shanghai, China).
2. Test materials: the ultrafine uniform-grained calcium phosphate bioceramic prepared in example 1 is numbered as ceramic a;
the superfine uniform grain calcium phosphate biological ceramic prepared when the pre-sintering temperature is 700 ℃ is numbered as ceramic B;
control materials: the preparation condition of the traditional calcium phosphate ceramic is that hydroxyapatite initial powder is directly subjected to cold isostatic pressing, and then is sintered at 1100 ℃ for 2 hours and then is cooled along with a furnace to prepare the calcium phosphate ceramic.
3. The test method comprises the following steps:
bone marrow mesenchymal stem cells (BMSCs) are recovered, passed through passages and proliferated. Good BMSCs were inoculated onto ceramic A, ceramic B and conventional calcium phosphate ceramic (75% ethanol sterilized), the material was co-cultured with the cells for 7 days, after which the cells were lysed and ALP viability of the cells was determined using an alkaline phosphatase (ALP) kit.
4. The test results are shown in fig. 6:
ALP viability results show that BMSCs exhibit higher ALP viability on ceramic A, ceramic B relative to conventional calcium phosphate ceramics. The test result shows that the superfine uniform grain calcium phosphate biological ceramic provided by the invention has excellent osteogenic activity.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of calcium phosphate bioceramic with ultrafine uniform grains is characterized by comprising the following steps:
s1, low-temperature presintering: pre-sintering the calcium phosphate initial powder at a low temperature to form a primary crystal phase;
s2, ball milling and centrifuging: performing wet ball milling treatment on the pre-sintered calcium phosphate powder, performing gradient centrifugation on the ball-milled slurry, and separating to obtain the calcium phosphate powder with small grain size and narrow distribution;
s3, forming: preparing the calcium phosphate powder obtained by ball milling and centrifugal optimization into a ceramic green body;
s4, two-step sintering: and (3) sintering the ceramic green body in two steps, and immediately quenching and rapidly cooling after the second-step sintering heat preservation is finished to obtain the calcium phosphate biological ceramic.
2. The method for preparing the ultrafine calcium phosphate bioceramic with uniform grains according to claim 1, wherein the low-temperature pre-sintering temperature in S1 is 500-900 ℃, and the pre-sintering time is 2-8 h.
3. The method for preparing the ultrafine uniform-grain calcium phosphate bioceramic according to claim 1 or 2, wherein in S2, a wet ball milling medium is absolute ethyl alcohol or/and water, the rotation speed is 300-1500 rpm, and the ball milling time is 5-30 h.
4. The method for preparing an ultrafine homogeneous grained calcium phosphate bioceramic according to claim 1 or 2, wherein the number of times of gradient centrifugation is 2 or more;
preferably, the centrifugation speeds are successively higher;
preferably, centrifuging the slurry after ball milling at 5000-6000 rpm, then centrifuging the supernatant for the second time at 8000-10000 rpm, centrifuging the supernatant obtained by the second centrifugation at 10000-12000 rpm, taking the precipitate, and drying to obtain the calcium phosphate powder with small grain size and narrow distribution;
preferably, the time of each centrifugation is 3-10 min, and more preferably 5 min.
5. The method for preparing the calcium phosphate bioceramic with ultrafine and uniform grains according to claim 1 or 2, wherein the particle size of the calcium phosphate powder obtained through ball milling and centrifugal optimization is 50-100 nm.
6. The method for preparing the ultrafine uniform grain calcium phosphate bioceramic according to claim 1 or 2, wherein in S4, the sintering temperature in the first step is 950-1150 ℃, and the holding time is 0-30 min;
or/and the temperature of the second sintering step is 650-950 ℃, and the heat preservation time is 2-40 h.
7. The method for preparing an ultra-fine uniform-grained calcium phosphate bioceramic according to claim 1 or 2, wherein the quenching rapid cooling process is an air-quenching rapid cooling process in S4.
8. A calcium phosphate bioceramic produced by the process of any one of claims 1 to 7.
9. The calcium phosphate bioceramic according to claim 8, wherein the calcium phosphate bioceramic grain size is 200nm or less.
10. The calcium phosphate bioceramic according to claim 8 or 9, wherein the compressive strength of the calcium phosphate bioceramic is 100-150 MPa.
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| CN115849957A (en) * | 2022-11-25 | 2023-03-28 | 南京航空航天大学 | Rapid repairing method for damage defect of ceramic matrix composite |
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