CN111481740A - High-dispersity amorphous calcium phosphate nano powder and preparation method and application thereof - Google Patents
High-dispersity amorphous calcium phosphate nano powder and preparation method and application thereof Download PDFInfo
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Abstract
The high-dispersity amorphous calcium phosphate nano powder comprises 1-5 parts of rare earth, 20-50 parts of calcium salt, 20-50 parts of water glass and 3-8 parts of sodium chloride. The preparation method comprises the steps of S1, mixing and dripping; s2, carrying out hydrothermal reaction at 200-210 ℃ for 30-60 min; s3, roasting at 250-300 ℃ for 5-15 min; s4, uniformly mixing; s5, carrying out hydrothermal reaction at 110-150 ℃ for 30-90 min; s6, filtering, drying and grinding. The invention is used as a biomedical 3D printing material. The invention overcomes the key technical bottleneck that ACP nano powder has poor dispersibility and low bone strength index. The electropositive lamellar crystal in the cluster prevents the cluster from disintegrating through electrostatic attraction and effectively prevents the ACP from spontaneously changing phase, and prevents the ACP cluster from approaching through electrostatic repulsion, so that the ACP nano powder is fundamentally prevented from agglomerating and is stably positioned in a nano scale, the bone strength index of the solid finished product is ensured to be high, and the clinical requirement of bone repair treatment is met.
Description
Technical Field
The invention relates to the field of 3D printing materials, in particular to high-dispersity amorphous calcium phosphate nano powder and a preparation method and application thereof.
Background
Amorphous Calcium Phosphate (ACP) is a thermodynamically metastable state of calcium phosphate, and is widely used as an implant material, a drug carrier, and the like of living bones such as human exoskeleton due to its characteristic advantages such as good biocompatibility, good osteoinductive effect, and bioactivity. However, ACP is unstable, particularly when exposed to water or acid, i.e., undergoes a rapid phase transition, and not only is it difficult to obtain a highly pure amorphous phase because it is rapidly transformed into a stable apatite at the initial stage of formation, but also it undergoes a number of spontaneous phase transition transformations in about one month even if it is collected within several minutes during the precipitation of ACP and then immediately freeze-dried sufficiently and stored in a vacuum at a low temperature. Therefore, the modified ACP is used as a powder material, water or dilute acid is used as a bonding solution, and the biological skeleton implant material with any shape can be prepared in a 3D printing mode, which is one of the current international hot spot technologies for rapid prototyping manufacturing, has already obtained primary clinical application in part of western developed countries, and shows extremely wide development potential. At present, the development of the domestic improvement field is in the starting stage, and the technology difference from foreign countries is very large.
The processes for preparing ACP nano-powder in the prior art mainly comprise a wet process and a dry process, and mainly comprise a coprecipitation method, a sol-gel method, a hydrothermal method and a mechanical method according to the preparation technical principle. However, it is difficult to obtain a modified ACP having high stability and high purity by any of the conventional production techniques.
In order to improve the stability and the purity of modified ACP, the invention patent of China with the application number of 201910172278.X adopts rare earth substances, silica sol, soluble magnesium salts, soluble aluminum salts, fluorine salts and the like as raw materials, prepares a zero-charge magnesium aluminum silicate auxiliary agent through a high-temperature hydrothermal reaction, and participates in the high-temperature water phase reaction of a calcium source and a phosphorus source to prepare the amorphous calcium phosphate nano powder material.
Although the technical scheme improves the stability and the purity of the existing modified ACP, the technical scheme does not consider the problems that the modified ACP powder is easy to agglomerate and is difficult to store in the storage process. The ACP nano powder is easy to agglomerate during storage, so that when the ACP nano powder is contacted with the liquid drops of the bonding solution in the 3D printing process, the hydration hardening reaction degree of the ACP is quickly reduced, and the bone strength index of an ACP/3D printed bone finished product is poor, which is a key technical problem in the technical field of ACP/3D printing.
Therefore, how to prepare the ACP nano powder for 3D printing with good dispersibility, good stability, high purity and excellent bone strength index is a technical problem which is urgently needed to be solved by related industries at home and abroad at present.
Disclosure of Invention
The primary object of the present invention is to provide an amorphous calcium phosphate nanopowder having high stability, high purity, good dispersibility, and excellent bone strength index, in view of the above drawbacks and disadvantages.
The invention also aims to provide a preparation method of the amorphous calcium phosphate nano powder with high dispersibility.
The invention further aims to provide application of the amorphous calcium phosphate nano powder with high dispersibility.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the high-dispersity amorphous calcium phosphate nano powder comprises 0.1-0.5 part by weight of electropositive layered silicate, 100-200 parts by weight of calcium salt and 100-200 parts by weight of phosphate; the electropositive layered silicate comprises, by weight, 1-5 parts of rare earth substances, 20-50 parts of calcium salts, 20-50 parts of water glass and 3-8 parts of sodium chloride.
As a further technical scheme of the invention, the electropositive layered silicate comprises 2-4 parts by weight of rare earth substances, 30-40 parts by weight of calcium salt, 30-40 parts by weight of water glass and 5 parts by weight of sodium chloride.
As a further technical scheme of the invention, the high-dispersity amorphous calcium phosphate nano powder also comprises 300-700 parts of pure water.
As a further technical scheme of the invention, the rare earth substance is Ce (NO)3)3、Ce2(SO4)3、CeCl3、Dy(NO3)3、Dy2(SO4)3Or DyCl3One or more of them in any combination.
As a further technical solution of the present invention, the calcium salt is Ca (NO)3)2Or CaCl2One or two of them can be arbitrarily combined.
As a further technical scheme of the invention, the modulus of the water glass is not less than 3.1.
As a further technical scheme of the invention, the phosphate is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate in any combination.
The preparation method of the high-dispersity amorphous calcium phosphate nano powder comprises the following steps of:
preparation of electropositive layered silicate
S1, fully and uniformly mixing rare earth substances, calcium salt and pure water, and slowly dripping water glass for at least 30 min;
s2, filtering a product after the dropwise addition is finished, adding a filter cake, sodium chloride and a proper amount of pure water into a hydrothermal reaction kettle, heating to 200-210 ℃ in a closed manner, and carrying out heat preservation reaction for 30-60 min;
s3, cooling to room temperature, discharging, filtering the product, and roasting the filter cake at 250-300 ℃ for 5-15 min to obtain the electropositive layered silicate;
b preparation of amorphous calcium phosphate nano powder
S4, dispersing the electropositive layered silicate in a proper amount of pure water, and then adding calcium salt and phosphate to uniformly mix;
s5, transferring the uniformly mixed materials into a hydrothermal reaction kettle, raising the temperature to 110-150 ℃ in a closed manner, and stirring for 30-90 min in a heat preservation manner;
and S6, cooling to room temperature, discharging, filtering, drying a filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not larger than 200 meshes to obtain the amorphous calcium phosphate nano powder.
In the technical scheme of the invention, the research of various analytical instruments such as XRD, FT-IR, AFM, TEM, SEM, EXAFS and the like and other characterization means proves and finds that:
mixing rare earth substance and calcium salt, and generating rare earth ion modified Ca (OH) under the action of salt ion (salting out)2Sol; slowly adding water glass dropwise, and gradually generating SiO under salting-out action2Sol of Ca (OH)2Step-by-step stacking with sol as coreAnd (6) stacking. Then, soluble salts which do not participate in the sol-gel process in the system are fully removed by adopting a filtering and water washing mode, and then the filter cake is re-dispersed in pure water to carry out high-temperature hydrothermal reaction. After the hydrothermal reaction is finished, filtering to obtain a filter cake, roasting the filter cake at high temperature, and aging the layered stacking structure to obtain the layered silicate.
In the process, the most important link is that soluble salts which do not participate in the sol-gel process in the system are sufficiently removed by adopting a filtration and water washing mode before the high-temperature hydrothermal reaction, otherwise, the electropositive layered silicate cannot be synthesized at all. In addition, the rare earth substance must be mixed with the calcium salt first, and the water glass must be added slowly for successful synthesis of the electropositive layered silicate. Meanwhile, the electropositive layered silicate cannot be successfully prepared at the hydrothermal reaction temperature of less than 200 ℃ or more than 210 ℃ or the roasting temperature of less than 250 ℃ or more than 300 ℃.
The electropositive layered silicate prepared by the step is similar to the layered structure of lithium magnesium silicate (commonly called 'hectorite') but has a brand new lattice chemical structure of ①, which is formed by sandwiching a rare earth ion/Ca-O trioctahedron between an upper layer of Si-O tetrahedron and a lower layer of Si-O tetrahedron (the typical structure of the lithium magnesium silicate is that the upper layer of Si-O tetrahedron and the lower layer of Si-O tetrahedron sandwich a layer of L i)+Mg-O trioctahedron). ② the layered structure exhibits a weak positive charge (lithium magnesium silicate exhibits a negative charge) due to the positive charge of the rare earth ions/Ca-O trioctahedron.
The hydration properties of the electropositive layered silicate prepared by the above steps are similar to those of lithium magnesium silicate, and the electropositive layered silicate can be fully swelled and exfoliated in water, so that a plurality of electropositive layered platelet colloids are formed. Under the high-temperature hydrothermal condition, calcium salt and phosphate are gradually randomly stacked by taking 1 or even a plurality of lamellar crystal colloids as templates to form ACP classical Posner clusters. If a layered silicate such as hydrotalcite (positive in layered charge) or magnesium lithium silicate (negative in layered charge) is used instead of the electropositive layered silicate, ACP cannot be synthesized.
After the hydrothermal reaction is finished, filtering and washing the mixture by water to fully remove salts which do not participate in the hydrothermal reaction and salts generated in the reaction process, and then drying the filter cake to constant weight in vacuum at the temperature of not higher than 80 ℃. In this stage, if the hydrothermal reaction temperature is less than 110 ℃ or more than 150 ℃, or the hydrothermal reaction time is less than 30min or more than 90min, high-purity ACP cannot be synthesized.
According to the radial distribution analysis of X-ray attenuation, the ACP cluster prepared by the technology contains a certain amount of electropositive lamellar platelets, but the diameter of the cluster is about 0.8nm and is slightly smaller than that of a classical Posner cluster (about 0.95 nm); the underlying mechanism of this abnormal phenomenon is not clear.
One of the core innovations of the invention is as follows: on one hand, the positive electric lamellar crystal guides the ACP to be synthesized smoothly, so that the high-purity ACP is obtained; on the other hand, the electropositive lamellar platelets firmly attract PO in the ACP structure through electrostatic attraction4 3-、HPO4 2-And (3) the negative ions are generated, so that the negative ions cannot be dissociated from the Posner clusters, and the spontaneous phase change conversion process of the ACP is fundamentally destroyed. Only with this new chemical structure (i.e., Posner clusters with a certain number of electronegative lamellar platelets inside), ACP is in a thermodynamically stable state.
Research proves that at the moment, the ACP cluster is small in volume (the diameter is about 0.8nm), so that electropositive lamellar platelets in the cluster can prevent the ACP clusters from approaching each other through electrostatic repulsion (if the volume of the ACP cluster reaches 0.95nm of a classical Posner cluster, the electrostatic repulsion is counteracted by a steric effect), and then ACP powder particles cannot agglomerate and grow, and the size of the ACP powder particles is kept at a nanometer level all the time; at the moment, the ACP can rapidly generate hydration reaction in the 3D printing process, and the prepared bone finished product has high bone strength index, so that the biggest key technical problems of poor ACP nano powder dispersibility and low bone strength index of the 3D printed bone finished product are thoroughly solved.
As a further technical scheme of the invention, the reaction time in the step S2 is 40-50 min; in the step S3, the roasting temperature is 270-280 ℃.
As a further technical scheme of the invention, in the step S5, the reaction temperature is 120-140 ℃ and the reaction time is 50-70 min.
The high-dispersity amorphous calcium phosphate nano powder is applied to biomedical 3D printing.
Compared with the prior art, the invention has the following beneficial effects:
the invention overcomes the key technical bottlenecks of poor dispersibility and low bone strength index of the modified ACP nano powder. The electropositive lamellar crystal in the cluster prevents the cluster from disintegrating through electrostatic attraction and effectively prevents the ACP from spontaneously changing phase, and prevents the ACP cluster from approaching through electrostatic repulsion, so that the ACP nano powder is fundamentally prevented from agglomerating and is stably positioned in a nano scale, the bone strength index of the ACP/3D printing bone finished product is high, and the clinical requirement of bone repair treatment is met.
The invention not only obtains high-purity ACP (up to 95 percent or more) by high-temperature hydrothermal synthesis, but also solves the technical problem that the ACP is easy to spontaneously change phase. The ACP prepared by the invention has a special brand new chemical structure, is in a thermodynamic stable state and has good stability. Whereas ACP produced by prior art processes is generally less than 90% pure and is very susceptible to phase change to apatite (the existing products rapidly undergo spontaneous phase changes even when stored under vacuum conditions).
Detailed Description
The present invention is further explained and illustrated by the following embodiments, which should be understood to make the technical solution of the present invention clearer and easier to understand, and not to limit the scope of the claims.
Example 1
The high-dispersibility modified amorphous calcium phosphate nano-powder for 3D printing and the preparation method thereof described in this embodiment 1 are prepared from the following raw material components in parts by mass according to the following steps:
(1) first 1 part of Ce (NO)3)320 parts of Ca salt (NO)3)2And 100 parts of pure water are fully and uniformly mixed, and then 20-50 parts of water glass (the modulus is 3.1) is slowly dripped, and the dripping time is controlled to be 30 min; after the completion of the dropwise addition, filtration was carried out and washing with pure water was carried out sufficiently, and the obtained filter cake, 5 parts of sodium chloride and 400 parts of pure water were put into a hydrothermal reaction vessel and then, denseThe temperature is closed to be raised to 200 ℃ and the reaction is carried out for 30min under the condition of heat preservation; stopping the reaction, cooling to room temperature, discharging, filtering to obtain a filter cake, and roasting the filter cake at 250 ℃ for 5min to obtain the electropositive layered silicate No. 1;
(2) then, 0.1 part of the electropositive layered silicate 1# prepared in the step (1) was completely dispersed in 500 parts of pure water, and then 100 parts of Ca (NO) was added3)2And 100 parts of diammonium hydrogen phosphate are fully and uniformly stirred, then the materials are completely transferred into a hydrothermal reaction kettle, and then the temperature is raised to 110 ℃ in a closed manner, and the materials are stirred and reacted for 30 min; and then stopping the reaction, cooling to room temperature, discharging, filtering and fully washing the reaction solution, drying a filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not more than 200 meshes to obtain the ACP nano powder No. 1.
Example 2
The high-dispersibility modified amorphous calcium phosphate nano-powder for 3D printing and the preparation method thereof described in this embodiment 2 are prepared from the following raw material components in parts by mass according to the following steps:
(1) firstly 2.2 parts of Ce2(SO4)32.8 parts of Dy (NO)3)325 parts of Ca (NO)3)225 parts of CaCl2And 100 parts of pure water are fully and uniformly mixed, and then 50 parts of water glass (the modulus is 3.4) is slowly dripped, and the dripping time is controlled to be 60 min; after the dropwise addition, filtering and fully washing with pure water, adding the obtained filter cake, 5 parts of sodium chloride and 400 parts of pure water into a hydrothermal reaction kettle, then heating to 210 ℃ in a sealed manner, and carrying out heat preservation reaction for 60 min; stopping the reaction, cooling to room temperature, discharging, filtering to obtain a filter cake, and roasting the filter cake at 300 ℃ for 15min to obtain the electropositive layered silicate 2 #;
(2) then, 0.5 part of the electropositive layered silicate 2# prepared in the step (1) was completely dispersed in 500 parts of pure water, and 90 parts of Ca (NO) was added3)2110 parts of CaCl250 parts of ammonium dihydrogen phosphate and 150 parts of potassium dihydrogen phosphate are fully and uniformly stirred, then the materials are completely transferred into a hydrothermal reaction kettle, and then the temperature is raised to 150 ℃ in a closed manner, and the materials are stirred and reacted for 90min under the condition of heat preservation; then the reaction is stopped andcooling to room temperature, discharging, filtering and fully washing the reaction solution, drying the filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not more than 200 meshes to obtain the ACP nano powder No. 2.
Example 3
The high-dispersibility modified amorphous calcium phosphate nano-powder for 3D printing and the preparation method thereof described in this embodiment 3 are prepared from the following raw material components in parts by mass according to the following steps:
(1) first 0.7 part of CeCl31.5 parts of Dy (NO)3)30.8 part of Dy2(SO4)313 parts of Ca (NO)3)217 parts of CaCl2And 100 parts of pure water are fully and uniformly mixed, 10 parts of water glass (modulus is 3.2) and 20 parts of water glass (modulus is 3.3) are slowly dripped, and the dripping time is controlled to be 40 min; after the dropwise addition, filtering and fully washing with pure water, adding the obtained filter cake, 5 parts of sodium chloride and 400 parts of pure water into a hydrothermal reaction kettle, then heating to 205 ℃ in a sealed manner, and carrying out heat preservation reaction for 40 min; stopping the reaction, cooling to room temperature, discharging, filtering to obtain a filter cake, and roasting the filter cake at 260 ℃ for 8min to obtain the electropositive layered silicate # 3;
(2) then, 0.2 part of the electropositive layered silicate # 3 prepared in the step (1) was completely dispersed in 500 parts of pure water, and 73 parts of Ca (NO) was added3)248 parts of CaCl2Fully and uniformly stirring 40 parts of ammonium dihydrogen phosphate, 30 parts of dipotassium hydrogen phosphate and 50 parts of disodium hydrogen phosphate, transferring all the materials into a hydrothermal reaction kettle, then hermetically heating to 120 ℃, and carrying out heat preservation and stirring reaction for 40 min; and then stopping the reaction, cooling to room temperature, discharging, filtering and fully washing the reaction solution, drying a filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not more than 200 meshes to obtain the ACP nano powder No. 3.
Example 4
The high-dispersibility modified amorphous calcium phosphate nano-powder for 3D printing and the preparation method thereof described in this embodiment 4 are prepared from the following raw material components in parts by mass according to the following steps:
(1) headFirstly, 1.3 parts of Ce2(SO4)31.7 parts of CeCl30.9 part of Dy (NO)3)30.1 part of Dy2(SO4)323 parts of Ca (NO)3)217 parts of CaCl2And 100 parts of pure water are fully and uniformly mixed, and then 15 parts of water glass (modulus is 3.1), 10 parts of water glass (modulus is 3.2) and 15 parts of water glass (modulus is 3.4) are slowly dripped, and the dripping time is controlled to be 50 min; after the dropwise addition, filtering and fully washing with pure water, adding the obtained filter cake, 5 parts of sodium chloride and 400 parts of pure water into a hydrothermal reaction kettle, then heating to 208 ℃ in a sealed manner, and carrying out heat preservation reaction for 50 min; stopping the reaction, cooling to room temperature, discharging, filtering to obtain a filter cake, and roasting the filter cake at 290 ℃ for 12min to obtain the electropositive layered silicate 4 #;
(2) then, 0.4 part of the electropositive layered silicate 4# prepared in the step (1) was completely dispersed in 500 parts of pure water, and 90 parts of Ca (NO) was added3)292 parts of CaCl2Fully and uniformly stirring 30 parts of diammonium hydrogen phosphate, 70 parts of dipotassium hydrogen phosphate, 40 parts of sodium dihydrogen phosphate and 40 parts of disodium hydrogen phosphate, transferring all the materials into a hydrothermal reaction kettle, then raising the temperature to 140 ℃ in a closed manner, and carrying out heat preservation stirring reaction for 80 min; and then stopping the reaction, cooling to room temperature, discharging, filtering and fully washing the reaction solution, drying a filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not more than 200 meshes to obtain the ACP nano powder No. 4.
Comparative example 1
This comparative example 1 is substantially the same as example 4 except that in step (1), 1.3 parts of Ce are first used2(SO4)31.7 parts of CeCl30.9 part of Dy (NO)3)30.1 part of Dy2(SO4)3And 100 parts of pure water are fully and uniformly mixed, and then 15 parts of water glass (modulus is 3.1), 10 parts of water glass (modulus is 3.2) and 15 parts of water glass (modulus is 3.4) are slowly dripped, and the dripping time is controlled to be 50 min; then, 23 parts of Ca (NO) was added3)217 parts of CaCl2(ii) a The other operation process parameters are completely consistent with those of the example 4, and the preparationThe powder of (2) is referred to as No. 5.
Comparative example 2
This comparative example 2 is substantially the same as example 4 except that in step (1), the addition mode of 15 parts of water glass (modulus 3.1), 10 parts of water glass (modulus 3.2) and 15 parts of water glass (modulus 3.4) is changed to one-time addition to the hydrothermal reaction kettle (i.e., slow dropwise addition is not adopted); the other operational process parameters were completely the same as in example 4, and the powder thus prepared was designated as No. 6.
Comparative example 3
This comparative example 3 is basically the same as example 4 except that in step (1), after the dropwise addition of the water glass is completed, the mixture is not filtered and is sufficiently washed with pure water, and is directly transferred to a hydrothermal reaction kettle for hydrothermal high-temperature reaction; the other operational process parameters were completely the same as in example 4, and the powder thus prepared was designated as No. 7.
Comparative example 4
This comparative example 4 was substantially the same as example 4 except that the hydrothermal reaction temperature in the step (1) was 190 ℃ and the other operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 8.
Comparative example 5
This comparative example 5 is substantially the same as example 4 except that the hydrothermal reaction temperature in the step (1) was 215 ℃ and the other operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 9.
Comparative example 6
This comparative example 6 was substantially the same as example 4 except that the cake firing temperature in the step (1) was 245 ℃ and the other operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 10.
Comparative example 7
This comparative example 7 was substantially the same as example 4 except that the cake calcination temperature in step (1) was 310 ℃ and the remaining operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 11.
Comparative example 8
This comparative example 8 was substantially the same as example 4 except that the hydrothermal reaction temperature in the step (2) was 105 ℃ and the other operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 12.
Comparative example 9
This comparative example 9 was substantially the same as example 4 except that the hydrothermal reaction temperature in the step (2) was 160 ℃ and the other operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 13.
Comparative example 10
This comparative example 10 is substantially the same as example 4 except that hydrotalcite was used in place of the electropositive layered silicate # 4 in step (2), and the remaining operational process parameters were completely the same as example 4, and the powder thus prepared was designated as No. 14.
Comparative example 11
This comparative example 11 is substantially the same as example 4 except that lithium magnesium silicate is used in the step (2) in place of the electropositive layered silicate # 4, and the remaining operational process parameters are completely the same as example 4, and the powder thus prepared is referred to as No. 15.
The nano-powder Nos. 1 to 15 prepared in the above examples, imported ACP nano-powder (model: Objet-CP1, specially stabilized; manufactured by 3D systems, USA) as powder materials, and 0.1mo L. L-1A dilute citric acid solution (bonding solution) was used to prepare a finished artificial bone solid product of 10mm × 10mm × 10mm by 3D printing, and the results of the relevant tests were obtained as shown in Table 1. 3D printing experimental conditions were 128 holes (diameter of about 0.05mm) in a Z310 model 3D printer (American Z Corporation), a piezoelectric batch type printing head, a layer thickness of 0.175mm, and a saturation of 0.7.
Table 1 comparative test data
As can be seen from Nos. 5 to 15 in Table 1: in the step (1), if the rare earth substance is not mixed with the calcium salt, or the water glass is not added slowly, or the filtration and washing are not performed sufficiently before the high-temperature hydrothermal reaction, or the parameters of the high-temperature hydrothermal reaction and the high-temperature roasting conditions do not meet the ranges defined by the invention, the electropositive layered silicate cannot be successfully prepared, and the ACP synthesis is not guided from the point of view. In the step (2), if a layered silicate such as hydrotalcite or lithium magnesium silicate is used instead of an electropositive layered silicate, or if the hydrothermal reaction parameters in this step do not fall within the ranges defined in the present invention, high-purity ACP cannot be successfully produced.
No. 1-No. 4 show that the modified ACP nano powder prepared by the method has excellent dispersibility, the powder particles are stably positioned in a nano scale (the particle size is not more than 807nm), and agglomeration does not occur during storage (after standing for one month, the particle size is only slightly increased), so that hydration reaction can smoothly occur during 3D printing, and the bone strength index of a 3D printed bone finished product prepared by the modified ACP nano powder is high and far exceeds that of ACP similar products imported from abroad. In addition, the ACP powder has high purity and good stability, is in a thermodynamic stable state, cannot undergo spontaneous phase change conversion (after standing for one month, the purity of imported similar commodities is reduced from 81% to 80%), and has extremely wide application prospect.
While the present invention has been described by way of examples, and not by way of limitation, other variations of the disclosed embodiments, as would be readily apparent to one of skill in the art, are intended to be within the scope of the present invention, as defined by the claims.
Claims (10)
1. A high-dispersity amorphous calcium phosphate nano powder is characterized in that: comprises 0.1-0.5 part of electropositive layered silicate, 100-200 parts of calcium salt and 100-200 parts of phosphate by weight; the electropositive layered silicate comprises, by weight, 1-5 parts of rare earth substances, 20-50 parts of calcium salts, 20-50 parts of water glass and 3-8 parts of sodium chloride.
2. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1, characterized by: the electropositive layered silicate comprises 2-4 parts of rare earth substances, 30-40 parts of calcium salt, 30-40 parts of water glass and 5-6 parts of sodium chloride by weight.
3. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1 or 2, characterized by: the high-dispersity amorphous calcium phosphate nano powder further comprises 300-700 parts of pure water.
4. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1, characterized by: the rare earth substance is Ce (NO)3)3、Ce2(SO4)3、CeCl3、Dy(NO3)3、Dy2(SO4)3Or DyCl3One or more of them in any combination.
5. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1, characterized by: the calcium salt is Ca (NO)3)2Or CaCl2One or a combination of both.
6. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1, characterized by: the modulus of the water glass is not less than 3.1.
7. The highly dispersible amorphous calcium phosphate nanopowder according to claim 1, characterized by: the phosphate is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or disodium hydrogen phosphate in any combination.
8. A method for preparing the highly dispersible amorphous calcium phosphate nanopowder according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
preparation of electropositive layered silicate
S1, fully and uniformly mixing rare earth substances, calcium salt and pure water, and slowly dripping water glass for at least 30 min;
s2, filtering a product after the dropwise addition is finished, adding a filter cake, sodium chloride and a proper amount of pure water into a hydrothermal reaction kettle, heating to 200-210 ℃ in a closed manner, and carrying out heat preservation reaction for 30-60 min;
s3, cooling to room temperature, discharging, filtering the product, and roasting the filter cake at 250-300 ℃ for 5-15 min to obtain the electropositive layered silicate;
b preparation of amorphous calcium phosphate nano powder
S4, dispersing the electropositive layered silicate in a proper amount of pure water, and then adding calcium salt and phosphate to uniformly mix;
s5, transferring the uniformly mixed materials into a hydrothermal reaction kettle, raising the temperature to 110-150 ℃ in a closed manner, and stirring for 30-90 min in a heat preservation manner;
and S6, cooling to room temperature, discharging, filtering, drying a filter cake at the temperature of not higher than 80 ℃ in vacuum to constant weight, and finally grinding until the granularity is not larger than 200 meshes to obtain the amorphous calcium phosphate nano powder.
9. The method for preparing highly dispersible amorphous calcium phosphate nanopowder according to claim 8, wherein: the reaction time in the step S2 is 40-50 min; in the step S3, the roasting temperature is 270-280 ℃; in the step S5, the reaction temperature is 120-140 ℃ and the reaction time is 50-70 min.
10. The use of the highly dispersible amorphous calcium phosphate nanopowder according to any one of claims 1 to 6, wherein: be applied to biomedical 3D printing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149190A (en) * | 2020-08-18 | 2022-03-08 | 中山职业技术学院 | Preparation method of high-biocompatibility alpha-tricalcium phosphate nano powder for 3D printing |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2361964A1 (en) * | 2010-02-25 | 2011-08-31 | The Procter & Gamble Company | Detergent composition |
| CN103079645A (en) * | 2010-09-10 | 2013-05-01 | 荷兰联合利华有限公司 | Composite particle active and method for making the same |
| CN103588212A (en) * | 2013-10-29 | 2014-02-19 | 清华大学 | Method for synthesizing delta-layered sodium disilicate by silicon tetrachloride |
| EP2717684A1 (en) * | 2011-06-10 | 2014-04-16 | Kurt Obermeier GmbH & Co. KG | Wood protection agent having improved penetration and long-term stability |
| CN105121350A (en) * | 2013-03-11 | 2015-12-02 | 巴斯夫欧洲公司 | Synthetic zinc hectorite via hydrothermal preparation |
| KR101741998B1 (en) * | 2015-12-15 | 2017-05-31 | 세종대학교 산학협력단 | Use of aminopropyl magnesium phyllosilicate or aminopropyl calcium phyllosilicate for promoting gene delivery of virus vector |
| CN108546396A (en) * | 2018-04-24 | 2018-09-18 | 东北林业大学 | The biodegradation material and preparation method thereof of nano inorganic oxide/silicic acid/cellulose multilayer structure composite enhancing |
| CN110483084A (en) * | 2019-09-16 | 2019-11-22 | 江苏瑞复达新材料有限公司 | A kind of calcium hexaluminate In-situ reaction high-temperature ceramic materials and preparation method thereof |
-
2020
- 2020-04-17 CN CN202010307939.8A patent/CN111481740A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2361964A1 (en) * | 2010-02-25 | 2011-08-31 | The Procter & Gamble Company | Detergent composition |
| CN103079645A (en) * | 2010-09-10 | 2013-05-01 | 荷兰联合利华有限公司 | Composite particle active and method for making the same |
| EP2717684A1 (en) * | 2011-06-10 | 2014-04-16 | Kurt Obermeier GmbH & Co. KG | Wood protection agent having improved penetration and long-term stability |
| CN105121350A (en) * | 2013-03-11 | 2015-12-02 | 巴斯夫欧洲公司 | Synthetic zinc hectorite via hydrothermal preparation |
| CN103588212A (en) * | 2013-10-29 | 2014-02-19 | 清华大学 | Method for synthesizing delta-layered sodium disilicate by silicon tetrachloride |
| KR101741998B1 (en) * | 2015-12-15 | 2017-05-31 | 세종대학교 산학협력단 | Use of aminopropyl magnesium phyllosilicate or aminopropyl calcium phyllosilicate for promoting gene delivery of virus vector |
| CN108546396A (en) * | 2018-04-24 | 2018-09-18 | 东北林业大学 | The biodegradation material and preparation method thereof of nano inorganic oxide/silicic acid/cellulose multilayer structure composite enhancing |
| CN110483084A (en) * | 2019-09-16 | 2019-11-22 | 江苏瑞复达新材料有限公司 | A kind of calcium hexaluminate In-situ reaction high-temperature ceramic materials and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A. WIECHEC ET AL: "The Study of Human Osteoblast-Like MG 63 Cells Proliferation on Resorbable Polymer-Based Nanocomposites Modified with Ceramic and Carbon Nanoparticles", 《ACTA PHYSICA POLONICA A》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149190A (en) * | 2020-08-18 | 2022-03-08 | 中山职业技术学院 | Preparation method of high-biocompatibility alpha-tricalcium phosphate nano powder for 3D printing |
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