CN112893832A - Ceramic particles and method for producing same - Google Patents

Ceramic particles and method for producing same Download PDF

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Publication number
CN112893832A
CN112893832A CN202010651574.0A CN202010651574A CN112893832A CN 112893832 A CN112893832 A CN 112893832A CN 202010651574 A CN202010651574 A CN 202010651574A CN 112893832 A CN112893832 A CN 112893832A
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CN
China
Prior art keywords
core
calcium
ceramic particles
modified layer
phosphorus
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CN202010651574.0A
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Chinese (zh)
Inventor
曾俊杰
张彦晧
王跃钧
蔡东霖
吕英诚
林秋丰
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Metal Industries Research and Development Centre
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Metal Industries Research and Development Centre
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Publication of CN112893832A publication Critical patent/CN112893832A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16Metallic particles coated with a non-metal
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Abstract

The invention provides a ceramic particle for forming an implant, which solves the problem that an anti-corrosion layer must be additionally formed on the outer surface of the conventional implant. The ceramic particle includes: a core formed of magnesium metal or magnesium alloy, the core having a particle size of 30 to 100 μm; and a modified layer covering the outer surface of the core, the modified layer containing calcium and phosphorus. The present invention further relates to a method for producing the ceramic particles.

Description

Ceramic particles and method for producing same
Technical Field
The present invention relates to a ceramic particle, and more particularly, to a modified ceramic particle, and a method for producing the same.
Background
Magnesium metal has light weight, density and elastic coefficient similar to periosteum, excellent mechanical property and biodegradability, so that magnesium alloy prepared by mixing magnesium metal and other metals has the potential of replacing titanium alloy and stainless steel as biomedical materials.
However, magnesium alloys have poor corrosion resistance and degrade too rapidly in vivo, so that the surface of the existing implants made of magnesium alloys is generally covered with a corrosion resistant layer formed of hydroxyapatite to prevent the existing implants from rapidly degrading after being implanted into the living body. However, since the difference between the mechanical properties of the anti-corrosion layer and the existing implant is large, when the anti-corrosion layer is damaged, the anti-corrosion layer is easy to fall off in a whole piece during the use process.
Therefore, there is a real need to improve the above problems.
Disclosure of Invention
In order to solve the above problems, the present invention provides a ceramic particle, which can be used to form an implant with good corrosion resistance without forming an additional corrosion-resistant layer.
It is another object of the present invention to provide a method for manufacturing ceramic particles, so as to form the ceramic particles.
The ceramic particles of the present invention may include: a core formed of magnesium metal or magnesium alloy, the core having a particle size of 30 to 100 μm; and a modified layer covering the outer surface of the core, the modified layer containing calcium and phosphorus.
Therefore, the ceramic particles of the present invention cover the modifying layer on the outer surface of the core, so that the implant made of the ceramic particles is not easy to cause abnormal reaction after being implanted into an organism, and can promote bone cells to climb on the implant, so that the implant can be tightly combined with bones, and the effect of the present invention is obtained. Moreover, because the ceramic particles comprise the modified layer, the outer surface of the implant formed by the ceramic particles does not need to additionally form an anti-corrosion layer, and the implant can have a good anti-corrosion effect, so that the effect of avoiding the complicated working procedures of the anti-corrosion layer can be realized; in addition, the implant does not have the anti-corrosion layer, so that the situation that the anti-corrosion layer falls off in a whole piece in the using process can be avoided, and the effect of improving the using convenience of the implant can be realized.
In the ceramic particles, the thickness of the modified layer can be between 0.1 and 5 mu m; thus, the modified layer with enough thickness can be ensured on the outer surface of the core, so that the ceramic particles have good properties of biocompatibility, osteoinductivity and the like.
In the ceramic particles of the present invention, the molar ratio of calcium to phosphorus in the modified layer may be between 1.0 and 1.8, for example, the modified layer may be formed of calcium hydrogen phosphate, hydroxyapatite or calcium phosphate; thus, the ceramic particles can have good properties such as biocompatibility and osteoinductivity.
The method for producing ceramic particles of the present invention may include: providing a core, wherein the core is formed by magnesium metal or magnesium alloy, and the particle size of the core is 30-100 μm; dissolving a calcium salt and a phosphorus salt in a solvent, and adding a chelating agent into the solvent to form a modified solution; and adding the core into the modifying solution to form a modified layer on the outer surface of the core at a temperature of 5-40 ℃, wherein the modified layer contains calcium and phosphorus.
Therefore, the temperature control can ensure that the modified layer can be uniformly formed on the outer surface of the core, so that the implant prepared from the obtained ceramic particles is not easy to cause abnormal reaction after being implanted into an organism, and can promote bone cells to climb on the implant, so that the implant can be tightly combined with bones, and the effect of the invention is achieved.
In the method for manufacturing the ceramic particles, the calcium salt can be calcium nitrate, calcium phosphate or calcium sulfate, the phosphorus salt can be monopotassium phosphate, sodium dihydrogen phosphate or magnesium phosphate, and the chelating agent can be ethylenediamine tetraacetic acid sodium or ethylenediamine; therefore, by selecting proper calcium salt and phosphorus salt and matching proper chelating agent, a modified layer formed by a specific compound can be formed on the outer surface of the core, so that the ceramic particles have good properties of biocompatibility, osteoinductivity and the like.
Drawings
FIG. 1: a cross-sectional view of a ceramic particle of an embodiment of the invention;
FIG. 2 a: in the test (a), an image of the core of the ceramic particle taken with a scanning electron microscope;
FIG. 2 b: in the test (a), an image of the ceramic particles photographed by a scanning electron microscope;
FIG. 2 c: FIG. 2b is a magnified image of the R region;
FIG. 3: in test (B), the corrosion rate line plots for each set of samples.
Description of the reference numerals
[ invention ] to provide
1 ceramic particles
11 core
12 modified layer
D particle diameter
T thickness.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below:
referring to fig. 1, a ceramic particle 1 according to an embodiment of the present invention may include a core 11 and a modified layer 12, wherein the modified layer 12 covers an outer surface of the core 11.
In particular, the core 11 may be formed of magnesium metal or magnesium alloy, such as magnesium alloy including metals such as calcium, zinc, manganese, cerium, thorium, or zirconium, thereby improving mechanical properties (e.g., yield strength, elongation, etc.) of the core 11.
The core 11 can be obtained by forming a molten metal into small droplets by a nozzle, cooling and solidifying the droplets, and the obtained core 11 can have a high sphericity (sphericity). In the present embodiment, the particle diameter D of the core 11 may be between 30 μm and 100 μm.
The modified layer 12 may contain calcium (Ca) and phosphorus (P), preferably the molar ratio (Ca/P ratio) of calcium to phosphorus may be 1.0-1.8And (3) removing the solvent. For example, the modified layer 12 may be made of calcium hydrogen phosphate (CaHPO)4) Hydroxyapatite (Ca)5(PO4)3(OH)) or calcium phosphate (Ca)3(PO4)2) And the implant made of the ceramic particles 1 is not easy to cause abnormal reaction after being implanted into an organism, can promote bone cells to climb on the implant, and can be tightly combined with bones due to the characteristics of biocompatibility (biocompability), osteoinductivity (osteointuition) and the like of the calcium and phosphorus-containing compound.
In this embodiment, workers can dissolve a calcium salt (calcium salt) and a phosphorus salt (phosphorus salt) in a solvent, and add a chelating agent (chelating agent) into the solvent to form a modified solution, wherein the calcium concentration and the phosphorus concentration of the modified solution are both between 0.05 mol/L and 0.5 mol/L. For example, the calcium salt may be calcium nitrate (Ca (NO)3)2) Calcium phosphate (Ca)3(PO4)2) Or calcium sulfate (CaSO)4) The phosphorus salt may be potassium dihydrogen phosphate (KH)2PO4) Sodium dihydrogen phosphate (NaH)2PO4) Or magnesium phosphate (Mg)3(PO4)2) Etc., the chelating agent may be sodium edetate (C)10H14N2Na2O8) Or ethylenediamine (C)2H4(NH2)2) And the solvent may be water or the like. In addition, the worker can select a specific calcium salt and a specific phosphorus salt, and adjust the calcium salt and the specific phosphorus salt to a predetermined ratio, so as to form the modified layer 12 from the specific calcium and phosphorus-containing compound.
Then, the core 11 is added into the modified solution, and stirred at 5-40 ℃ for 5-30 minutes, so as to form the modified layer 12 on the outer surface of the core 11 and obtain the ceramic particles 1, wherein the thickness T of the modified layer is 0.1-5 μm.
It should be noted that the ceramic particles 1 of the present embodiment may be formed into an implant (e.g., bone nail, dental implant, bone plate, etc.) by injection molding (injection molding), powder metallurgy (powder metallurgy), 3D printing (3D printing), or compression molding (compression molding), and the implant may be implanted into a body of a living body, and thus may be applied to reconstruction of teeth, bones, joints, etc. of the living body. At this time, since the implant is formed of the ceramic particles 1 of the present embodiment, there is no need to additionally form an anti-corrosion layer on the outer surface of the implant, i.e., the implant has a good anti-corrosion effect.
To confirm that the ceramic particles 1 can be produced by the method for producing the ceramic particles 1 and that the ingot formed from the ceramic particles 1 has a superior corrosion resistance effect, the following tests were performed:
(A) image taken by scanning electron microscope
In the test, magnesium alloy particles formed by a gas atomization forming method are taken as the core 11, then the modifying solution (containing calcium nitrate, potassium dihydrogen phosphate and sodium ethylene diamine tetraacetic acid, and the pH value is adjusted to be 4-6) is added into the core 11 to form the modifying layer 12 on the outer surface of the core 11, and the ceramic particles 1 are obtained after filtration and drying.
Then, images of the core 11 and the ceramic particle 1 are taken by a scanning electron microscope (scanning electron microscope), and as a result, as shown in fig. 2a, 2b, and 2c, respectively, it is shown that the roughness of the outer surface of the ceramic particle 1 is different from the roughness of the outer surface of the core 11, indicating that the modified layer 12 has indeed been formed on the outer surface of the core 11.
(B) Evaluation of Corrosion resistance
In this test, the ingots formed from the ceramic particles 1 were used as group B1, the ingots formed from the core 11 were used as group B0, the ingots of groups B0 and B1 were placed in Simulated Body Fluid (SBF) respectively, and the daily hydrogen production was recorded, and the corrosion resistance of the ingots of groups B0 and B1 was evaluated, as shown in fig. 3, the hydrogen production of the ingots formed from the ceramic particles 1 was significantly lower than that of the ingots formed from the core, indicating that the ingots formed from the ceramic particles 1 had better corrosion resistance.
In summary, the ceramic particle 1 of the present invention, through the modified layer covering the outer surface of the core, makes the implant made of the ceramic particle 1 not only not easily cause abnormal reaction after being implanted into an organism, but also can promote bone cells to climb on the implant, so that the implant can be tightly combined with the bone, which is the efficacy of the present invention.
Moreover, because the ceramic particles 1 comprise the modified layer, the outer surface of the implant formed by the ceramic particles 1 can have good corrosion resistance effect without additionally forming a corrosion resistance layer, thereby realizing the effect of avoiding the complicated working procedures of the corrosion resistance layer; in addition, the implant does not have the anti-corrosion layer, so that the situation that the anti-corrosion layer falls off in a whole piece in the using process can be avoided, and the effect of improving the using convenience of the implant can be realized.
In the method for manufacturing the ceramic particle 1 of the present invention, since the modified layer can be uniformly formed on the outer surface of the core by controlling the temperature, the implant manufactured by using the obtained ceramic particle 1 is not likely to cause abnormal reaction after being implanted into a living body, and can promote bone cells to climb on the implant, so that the implant can be tightly bonded to the bone, which is the efficacy of the present invention.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A ceramic particle, comprising:
a core formed of magnesium metal or magnesium alloy, the core having a particle size of 30 to 100 μm; and
a modified layer covering the outer surface of the core, the modified layer comprising calcium and phosphorus.
2. The ceramic particle of claim 1, wherein the thickness of the modified layer is between 0.1 μm and 5 μm.
3. The ceramic particle of claim 1, wherein the molar ratio of calcium to phosphorus in the modified layer is between 1.0 and 1.8.
4. The ceramic particle of claim 3, wherein the modified layer is formed from calcium hydrogen phosphate, hydroxyapatite or calcium phosphate.
5. A method for producing ceramic particles, comprising:
providing a core, wherein the core is formed by magnesium metal or magnesium alloy, and the particle size of the core is 30-100 μm;
dissolving a calcium salt and a phosphorus salt in a solvent, and adding a chelating agent to the solvent to form a modified solution; and
adding the core into the modifying solution, and forming a modifying layer on the outer surface of the core at the temperature of 5-40 ℃, wherein the modifying layer contains calcium and phosphorus.
6. The method for producing ceramic particles according to claim 5, wherein the calcium salt is calcium nitrate, calcium phosphate or calcium sulfate.
7. The method of claim 5, wherein the phosphorus salt is potassium dihydrogen phosphate, sodium dihydrogen phosphate, or magnesium phosphate.
8. The method of claim 5, wherein the chelating agent is sodium ethylenediamine tetraacetate or ethylenediamine.
CN202010651574.0A 2019-12-03 2020-07-08 Ceramic particles and method for producing same Pending CN112893832A (en)

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TW108144127A TWI757665B (en) 2019-12-03 2019-12-03 Method for manufacturing implant

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508682A (en) * 1982-04-02 1985-04-02 Toyota Jidosha Kabushiki Kaisha Method for making composite material including matrix metal and metal cored ceramic surfaced fine powder material
US6582763B1 (en) * 1999-01-29 2003-06-24 Nisshin Seifun Group Inc. Process for producing oxide coated fine metal particles
DE102007027971A1 (en) * 2007-06-19 2008-12-24 Robert Bosch Gmbh Method for manufacturing stabilized particles, involves sheathing core with layer of ceramic precursor compound, where ceramic precursor compound is converted into ceramic layer
CN105063618A (en) * 2015-08-22 2015-11-18 山东建筑大学 Method for preparing hydroxyapatite film layer on magnesium alloy surface
CN107236940A (en) * 2017-05-12 2017-10-10 重庆大学 A kind of preparation method of calcium phosphate coated magnesium powder
WO2019002277A1 (en) * 2017-06-27 2019-01-03 Aap Implantate Ag Magnesium alloy, biodegradable implant and method for producing a biodegradable implant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104127910B (en) * 2014-07-15 2015-12-30 东南大学 There is absorbable magnesium alloy staple and the preparation method of anti-inflammation function

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508682A (en) * 1982-04-02 1985-04-02 Toyota Jidosha Kabushiki Kaisha Method for making composite material including matrix metal and metal cored ceramic surfaced fine powder material
US6582763B1 (en) * 1999-01-29 2003-06-24 Nisshin Seifun Group Inc. Process for producing oxide coated fine metal particles
DE102007027971A1 (en) * 2007-06-19 2008-12-24 Robert Bosch Gmbh Method for manufacturing stabilized particles, involves sheathing core with layer of ceramic precursor compound, where ceramic precursor compound is converted into ceramic layer
CN105063618A (en) * 2015-08-22 2015-11-18 山东建筑大学 Method for preparing hydroxyapatite film layer on magnesium alloy surface
CN107236940A (en) * 2017-05-12 2017-10-10 重庆大学 A kind of preparation method of calcium phosphate coated magnesium powder
WO2019002277A1 (en) * 2017-06-27 2019-01-03 Aap Implantate Ag Magnesium alloy, biodegradable implant and method for producing a biodegradable implant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王勇等: "二水磷酸氢钙包覆镁粉的组织及其在NaCl溶液中的腐蚀行为", 《材料导报》 *

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