Method for synthesizing apatite powder by laser

文档序号:148452 发布日期:2021-10-26 浏览:45次 中文

阅读说明:本技术 利用激光的磷灰石粉末合成方法 (Method for synthesizing apatite powder by laser ) 是由 全豪珽 严胜勋 金有燦 韩衡燮 玉明烈 徐铉善 石铉光 于 2021-02-03 设计创作,主要内容包括:提供一种利用激光的磷灰石粉末合成方法,其包括如下步骤:将基板浸渍于磷灰石形成用前体溶液中;向浸渍于所述磷灰石形成用前体溶液中的基板上的区域照射激光束;以及获得在所述磷灰石形成用前体溶液中生成的磷灰石粉末。(Provided is a method for synthesizing apatite powder by using laser, which comprises the following steps: immersing a substrate in a precursor solution for apatite formation; irradiating a laser beam to a region on the substrate immersed in the precursor solution for apatite formation; and obtaining an apatite powder produced in the apatite-forming precursor solution.)

1. A method for synthesizing apatite powder by using laser comprises the following steps:

(a) immersing a substrate in a precursor solution for apatite formation;

(b) irradiating a laser beam to a region on the substrate immersed in the precursor solution for apatite formation; and

(c) obtaining an apatite powder produced in the apatite-forming precursor solution.

2. The method for synthesizing apatite powder using laser according to claim 1, wherein,

In the step (c), a apatite powder represented by chemical formula 1 is synthesized,

chemical formula 1:

(M1)a(M2)10-a(ZO4)6(X)2

wherein M is1、M2Are each selected from Ca2+、Pb2+、Sr2+、Mg2+、Fe2+、Mn2+、Cd2+、Ba2+、Co2+、Ni2+、Cu2+、Zn2+、Sn2+、Eu2+、Na+、K+、Li+、Rb+、NH4 +、La3+、Ce3+、Sm3+、Eu3+、Y3+、Bi3+、Cr3+、Th4+、U4+And U6+In the above-mentioned manner, the first and second substrates are,

ZO4is selected from PO4 3-、AsO4 3-、SiO4 4-、VO4 3-、CrO4 3-、CrO4 2-、MnO4 3-、SO4 2-、SeO4 2-、BeF4 2-、GeO4 4-、ReO5 3-、SbO3F4-、SiON5-、BO4 5-、BO3 3-And CO3 2-In the above-mentioned manner, the first and second substrates are,

x is selected from F-、OH-、Cl-、O2 -、O3 -、NCO-、BO2 -、Br-、I-、NO2 -、NO3 -、CO3 2-、O2 2-、O2-、S2-、NCN2-And NO2 2-In the above-mentioned manner, the first and second substrates are,

a is a real number between 0 and 10.

3. The method for synthesizing apatite powder using laser according to claim 2, wherein,

in the step (a), M is dissolved in the apatite-forming precursor solution1Ion, M2Ions and ZO4Ions.

4. The method for synthesizing apatite powder using laser according to claim 1, wherein,

when the apatite-forming precursor solution contains Ca2+Ions and PO4 3-When ionized, hydroxyapatite powder is formed in said step (c).

5. The method for synthesizing apatite powder using laser according to claim 1, wherein,

when the apatite-forming precursor solution contains Mg2+Ionically, forming a apatite powder in said step (c) of hydroxyapatite, Mg-containing apatite, whitlockite and combinations thereof.

6. The method for synthesizing apatite powder using laser according to claim 1, wherein,

the size of the apatite powder is controlled by adjusting the concentration of the apatite-forming precursor solution.

7. The method for synthesizing apatite powder using laser according to claim 1, wherein,

the step (b) includes the step of adjusting the laser beam irradiation time to control the size of the generated apatite powder.

8. The method for synthesizing apatite powder using laser according to claim 1, wherein,

the step (b) includes the step of adjusting the laser beam output power to control the size of the generated apatite powder.

9. The method for synthesizing apatite powder using laser according to claim 1, wherein,

controlling the composition of the apatite powder by adjusting the composition of the apatite forming precursor solution.

10. The method for synthesizing apatite powder using laser according to claim 2, wherein,

(M) of the apatite powder is controlled by adjusting the concentration of the apatite-forming precursor solution1+M2)/ZO4And (4) the ratio.

11. The method for synthesizing apatite powder using laser according to claim 1, wherein,

and controlling the crystallinity of the apatite powder by adjusting the power of the laser beam.

12. The method for synthesizing apatite powder using laser according to claim 1, wherein,

and controlling the crystallinity of the apatite powder by adjusting the pulse width of the laser beam.

Technical Field

The present invention relates to a method for synthesizing apatite powder using laser, and more particularly, to a method for forming apatite powder by immersing a substrate in a precursor solution for apatite formation and irradiating laser thereto.

Background

As the most widely used medical metal material, titanium-based alloys have a low elastic modulus and outstanding biocompatibility, and are more excellent in corrosion resistance and the like than the previously used bio-metals. However, it cannot directly induce bone formation due to its biological inertness, requires a considerable treatment time to achieve osseointegration, and the naturally formed oxidized powder, which is thin in thickness, rapidly disappears, thereby failing to guide the regeneration of adjacent bone tissue.

Therefore, the implant surface treatment is used to impart a biological activity to solve the problem that the implant cannot be directly bonded to the bone and the problem that the implant is loosened to shorten the period of bone bonding. The surface treatment of titanium, which is used as a main material of an implant, is being performed in a physical, chemical method to further improve bioactivity, thereby shortening the healing period after the implant is implanted into a human body, and research on more effective surface treatment is being continuously conducted.

At this time, hydroxyapatite was used as a material for surface treatment of the titanium surface. Hydroxyapatite (hydroxyapatite) has also been used as a bone tissue graft or a bone regeneration material as a basic component constituting hard tissues of the human body. The chemical structure of the hydroxyapatite is Ca10(PO4)6(OH)2Hydroxyapatite in enamel of a human body is mainly distributed in the outermost enamel with the thickness of about 1-2 mm. The hydroxyapatite can show remineralization effect, so that the hydroxyapatite has the function of filling tiny gaps of decalcified enamel.

In addition to the above-mentioned implant surface treatment, apatite is also required to have a suitable particle composition and particle size according to various application fields to provide characteristics according to the use. Conventionally, needle-shaped or plate-shaped apatite particles have been produced mainly by a solid-phase reaction method and a hydrothermal synthesis method. However, these prior methods have a number of problems.

The solid-phase reaction method has problems in that the heat treatment temperature is high at about 800 to 1200 ℃, and therefore, the particles to be produced are increased to several tens of micrometers, and complicated post-steps such as mixing, calcining, and pulverizing are required after the reaction, and thus, it cannot be an industrially advantageous method.

On the other hand, the hydrothermal synthesis method is a method of generally reacting amorphous precipitated Calcium Phosphate (Calcium Phosphate) in an autoclave at a temperature ranging from about 150 to 250 ℃, and requires two steps of precipitation and hydrothermal synthesis, and also requires mixing of various additives, and the process itself is complicated, thus causing a problem in mass production.

Disclosure of Invention

Technical problem

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for synthesizing an apatite powder by irradiating a surface of a base material immersed in a precursor solution for forming apatite with laser light.

However, this technical problem is exemplary, and the scope of the present invention is not limited thereto.

Technical scheme

According to an aspect of the present invention for achieving the above object, there is provided a method for synthesizing a apatite powder using a laser, including the steps of: (a) immersing a substrate in a precursor solution for apatite formation; (b) irradiating a laser beam to a region on the substrate immersed in the precursor solution for apatite formation; and (c) obtaining an apatite powder produced in the apatite-forming precursor solution.

In addition, according to an embodiment of the present invention, the apatite powder represented by chemical formula 1 can be synthesized in the step (c).

Chemical formula 1:

(M1)a(M2)10-a(ZO4)6(X)2

wherein M is1、M2Are each selected from Ca2+、Pb2+、Sr2+、Mg2+、Fe2+、Mn2+、Cd2+、Ba2+、Co2+、Ni2+、Cu2+、Zn2+、Sn2+、Eu2+、Na+、K+、Li+、Rb+、NH4 +、La3+、Ce3+、Sm3+、Eu3+、Y3+、Bi3+、Cr3+、Th4+、U4+And U6+In the above-mentioned manner, the first and second substrates are,

ZO4is selected from PO4 3-、AsO4 3-、SiO4 4-、VO4 3-、CrO4 3-、CrO4 2-、MnO4 3-、SO4 2-、SeO4 2-、BeF4 2-、GeO4 4-、ReO5 3-、SbO3F4-、SiON5-、BO4 5-、BO3 3-And CO3 2-In the above-mentioned manner, the first and second substrates are,

x is selected from F-、OH-、Cl-、O2 -、O3 -、NCO-、BO2 -、Br-、I-、NO2 -、NO3 -、CO3 2-、O2 2-、O2-、S2-、NCN2-And NO2 2-In the above-mentioned manner, the first and second substrates are,

a is a real number between 0 and 10.

Further, according to an embodiment of the present invention, in the step (a), M may be dissolved in the apatite-forming precursor solution1Ion, M2Ions and ZO4Ions.

In addition, according to an embodiment of the present invention, when the apatite-forming precursor solution contains Ca2+Ions and PO4 3-When ionic, capable of forming a hydroxyapatite powder in said step (c).

Further, according to an embodiment of the present invention, when the apatite-forming precursor solutionContaining Mg2+Ionic, capable of forming a apatite powder in said step (c) of hydroxyapatite, Mg-containing apatite, whitlockite (whitlockite) and combinations thereof.

In addition, according to an embodiment of the present invention, the size of the apatite powder may be controlled by adjusting the concentration of the apatite-forming precursor solution.

In addition, according to an embodiment of the present invention, the step (b) may include a step of adjusting a laser beam irradiation time to control a size of the generated apatite powder.

Further, according to an embodiment of the present invention, the step (b) may include a step of adjusting laser beam output power to control a size of the generated apatite powder.

In addition, according to an embodiment of the present invention, the composition of the apatite powder may be controlled by adjusting the composition of the apatite forming precursor solution. Further, according to an embodiment of the present invention, (M) of the apatite powder may be controlled by adjusting the concentration of the apatite-forming precursor solution1+M2)/ZO4And (4) the ratio.

In addition, according to an embodiment of the present invention, the crystallinity of the apatite powder may be controlled by adjusting the power of the laser beam.

In addition, according to an embodiment of the present invention, the crystallinity of the apatite powder may be controlled by adjusting the pulse width of the laser beam.

Advantageous effects

According to the above-described embodiment of the present invention, there is an effect that the surface of the substrate immersed in the precursor solution for apatite formation can be irradiated with laser light to synthesize the apatite powder having the adjusted composition and size.

However, the above-described problems are merely examples, and the scope of the present invention is not limited thereto.

Drawings

Fig. 1 is an SEM image of a apatite powder formed by laser power, and a plot of the size of the apatite powder formed as a function of laser power, according to an embodiment.

FIG. 2 is a graph showing the size of apatite formed by the concentration of a precursor solution for apatite formation and the laser irradiation time according to an embodiment.

Fig. 3 is an SEM image of a whitlockite (whitlockite) crystal produced according to an example.

FIG. 4 is an SEM image of apatite crystals produced according to an example and a comparative example.

FIG. 5 is a graph showing the size and growth rate of apatite crystals produced according to an example and a comparative example.

FIG. 6 is an SEM image of Mg-containing apatite crystals produced according to an example and the result of Mg content analysis.

FIGS. 7 to 9 show the results of electron microscope and XRD measurement of apatite in one example.

FIG. 10 is EDS measurements after apatite was generated according to an example.

Fig. 11 is XRD and electron microscopy measurements of the synthetic apatite powder with the laser power adjusted in one embodiment.

FIG. 12 is an XRD and electron microscopy measurement of a synthetic apatite powder with the laser pulse width adjusted in one embodiment.

Detailed Description

The following detailed description of the invention refers to the accompanying drawings, which illustrate specific embodiments by way of example, in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It is to be understood that the various embodiments of the invention are distinct from each other and are not necessarily mutually exclusive. For example, particular shapes, structures, and characteristics described herein may be associated with one embodiment and may be implemented in other embodiments without departing from the spirit and scope of the present invention. It is to be understood that the position or arrangement of each component in each disclosed embodiment may be modified without departing from the spirit and scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims and equivalents thereof, as appropriate. Like reference numerals in the drawings refer to the same or similar functionality in various respects, and may be exaggerated for convenience.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily practice the invention.

The method for synthesizing the apatite powder of one embodiment of the present invention includes the following steps: (a) immersing a substrate in a precursor solution for apatite formation; (b) irradiating a laser beam to a region on the substrate immersed in the precursor solution for apatite formation; and (c) obtaining an apatite powder produced in the apatite-forming precursor solution.

The substrate may be a material having a apatite film formed on the surface thereof, and may be a bio-metal, for example. For example, any one selected from titanium, titanium alloys, magnesium, and magnesium alloys may be used for the substrate. In addition, as the metal material or the ceramic material, a material which is required to form a apatite film may be used.

In the present invention, the apatite powder containing the ions contained in the apatite-forming precursor solution is formed by laser irradiation, and therefore the kind of the ions contained in the apatite-forming precursor solution is not particularly limited. In one embodiment, the apatite-forming precursor solution may contain Ca as a solution for supplying a raw material for producing apatite 2+、Pb2+、Sr2+、Mg2+、Fe2+、Mn2+、Cd2+、Ba2+、Co2+、Ni2+、Cu2+、Zn2+、Sn2+、Eu2+、Na+、K+、Li+、Rb+、NH4 +、La3 +、Ce3+、Sm3+、Eu3+、Y3+、Bi3+、Cr3+、Th4+、U4+And U6+And is selected from PO4 3-、AsO4 3-、SiO4 4-、VO4 3-、CrO4 3-、CrO4 2-、MnO4 3-、SO4 2-、SeO4 2-、BeF4 2-、GeO4 4-、ReO5 3-、SbO3F4-、SiON5-、BO4 5-、BO3 3-And CO3 2-An anion of (1). Additionally, may further comprise a compound selected from F-、OH-、Cl-、O2 -、O3 -、NCO-、BO2 -、Br-、I-、NO2 -、NO3 -、CO3 2-、O2 2-、O2-、S2-、NCN2-And NO2 2-Of (b) is (b). When the apatite-forming precursor solution containing the ions is used, an apatite powder represented by chemical formula 1 can be synthesized in the apatite-forming precursor solution.

Chemical formula 1:

(M1)a(M2)10-a(ZO4)6(X)2

wherein M is1、M2Are each selected from Ca2+、Pb2+、Sr2+、Mg2+、Fe2+、Mn2+、Cd2+、Ba2+、Co2+、Ni2+、Cu2+、Zn2+、Sn2+、Eu2+、Na+、K+、Li+、Rb+、NH4 +、La3+、Ce3+、Sm3+、Eu3+、Y3+、Bi3+、Cr3+、Th4+、U4+And U6+ZO is one of4Is selected from PO4 3-、AsO4 3-、SiO4 4-、VO4 3-、CrO4 3-、CrO4 2-、MnO4 3-、SO4 2-、SeO4 2-、BeF4 2-、GeO4 4-、ReO5 3-、SbO3F4-、SiON5-、BO4 5-、BO3 3-And CO3 2-X is selected from F-、OH-、Cl-、O2 -、O3 -、NCO-、BO2 -、Br-、I-、NO2 -、NO3 -、CO3 2-、O2 2-、O2-、S2-、NCN2-And NO2 2-A is a real number between 0 and 10. That is, the apatite powder containing ions dissolved in the apatite-forming precursor solution can be formed in the solution by laser irradiation.

Hereinafter, an example of the precursor solution for producing apatite includes Ca2+Ions and PO4 3-The precursor solution of the ions is described in more detail. For example, containing Ca2+Ions and PO4 3-The precursor Solution of ions may be one selected from the group consisting of solutions containing inorganic components of DMEM (Dulbecco Modified Eagle Medium), HBSS (Hank's Balanced Salt Solution), HBP (Human plasma: Human blood plasma), and SBF (Simulated body fluid). Ca which can convert the apatite-forming precursor solution 2+Ions and PO4 3-The concentration of the ions is increased by 1 to 400 times and then used to promote the formation of apatite. However, the present invention is not limited thereto as long as the concentration of the precursor solution can be adjusted according to the purpose of synthesis.

When a laser beam having high energy is irradiated onto the surface of a substrate immersed in a precursor solution for apatite formation, Ca in the precursor solution can be caused to exist2+Ion and PO4 3-The reaction of the ions is activated, thereby forming a apatite powder. Subsequently, a molded body may be formed by separating the produced apatite powder from the solution and solidifying or the like.

In the past, the apatite powder is synthesized by methods such as solid phase synthesis, liquid phase synthesis, gas phase synthesis, hydrothermal synthesis and the like, and the existing method has the problems of complex process and high-temperature heat treatment. In contrast, according to the embodiment of the present invention, it is possible to irradiate a laser beam to a region on a substrate in a precursor solution to form a apatite film on the substrate while forming apatite powder in the solution. Since the thus-produced apatite powder can be separated and dried, and products having various shapes can be produced by subsequent molding, the utilization rate is higher than that when the product is formed as a coating film.

As an energy supply source for supplying energy for forming apatite, the laser generator may use, for example, an Ytterbium Nanosecond Pulsed laser (Ytterbium Nanosecond Pulsed) generator or a femtosecond Pulsed laser (femtosecond laser) generator. At this time, the nanosecond laser means a laser having a pulse time of 10 nanoseconds-9Laser with short pulse width of second, femtosecond laser means 10-15A very short pulse width of the laser in seconds. However, the present invention is not limited thereto, and may be any laser light that can apply sufficient energy to the precursor solution to generate apatite.

The concentration of the precursor solution for apatite formation, the conditions of the laser beam, for example, the power of the laser beam, the irradiation time, and the like can be controlled to change the size of the resulting apatite powder.

The composition and concentration of the apatite-forming precursor solution can be adjusted to change the composition of the apatite powder. For example, when the apatite-forming precursor solution contains Mg2+When ionic, can be based on Mg2+The ion content to form any one of apatite powder of hydroxyapatite, Mg-containing apatite, whitlockite (whitlockite), and combinations thereof. As another example, the concentration of the precursor solution for apatite formation can be adjusted to control the (M) of the apatite powder 1+M2)/ZO4And (4) the ratio.

According to the embodiments of the present invention, the crystallinity (crystallinity) of the apatite powder can be adjusted by controlling the laser beam irradiation conditions, for example, the power, pulse width, wavelength, pulse energy, repetition rate, irradiation time, and the like of the laser.

In the following, a number of examples are described, which are intended to aid in the understanding of the present invention. However, the following embodiments are only for assisting understanding of the present invention, and the present invention is not limited to the following embodiments.

Examples

Titanium or magnesium is used for the substrate. DMEM with a concentration increased by 100 to 400 times is put into a precursor solution immersion part positioned on the upper part of the PDMS template on which the substrate is fixed. Then, a laser beam was irradiated to the surface of the substrate with an Ytterbium nanosecond pulsed laser (Ytterbium pulsed fiber laser) to form a apatite powder. The power of the laser beam is selected from the range of 1W to 15W, and the irradiation time is selected from the range of 15 minutes to 30 minutes.

Examples of the experiments

FIG. 1 is a result of analyzing the size of the synthesized apatite powder according to the laser power, and it can be confirmed that the size of the synthesized powder is about 50nm to 6000nm when the power is 1W to 15W. It was confirmed that the higher the laser irradiation energy was, the larger the size of the generated apatite powder was.

FIG. 2 is a graph showing the size of apatite formed according to the concentration of the precursor solution for apatite formation and the laser irradiation time. It was confirmed that the larger the concentration of the precursor solution, the longer the laser irradiation time, and the larger the size of the apatite powder formed. When the magnesium substrate is irradiated with laser light, the size of the formed apatite powder is smaller than that of the titanium substrate. Therefore, even when the same energy of laser light is irradiated, the degree of temperature rise can be expected to vary depending on the substrate.

FIG. 3 is an SEM image of a whitlockite (whitlockite) crystal produced from an apatite-forming precursor solution containing Mg ions. This confirmed that apatite crystals were formed by the laser beam.

FIGS. 4 and 5 are graphs showing images and crystal sizes of apatite crystals generated according to an example and a comparative example. FIGS. 4 (a) and (B) are electron microscope images of crystals formed by synthesizing whitlockite (whitlockite), which is apatite containing Mg ions, by hydrothermal synthesis and crystals grown for two weeks (refer to Jang, Hae Lin, et al. "Phase transformation from hydro xyapatite to the secondary bone mineral, whitlockite." Journal of Materials Chemistry B3.7 (2015): 1342-1349). Fig. 4 (c) is an electron microscope image of a crystal formed by synthesizing whitlockite (whitlockite), which is an apatite containing Mg ions, by laser irradiation.

In fig. 5 (a), the size of the whitlockite (whitlockite) crystals synthesized by hydrothermal synthesis was about 87nm and the size of the crystals grown for two weeks was about 212nm, whereas the size of the whitlockite (whitlockite) crystals synthesized by laser light for 15 minutes was about 1759nm, which indicates that crystals having a size of about 8 times as small as the minimum and 20 times as large as the maximum can be formed. Fig. 5 (b) shows a "crystal growth rate (growth rate)" obtained by dividing the crystal size by the reaction time, and the method using a laser beam has a rate about 11147 times faster than the crystal growth rate by the hydrothermal synthesis method.

FIG. 6 is an SEM image of the produced Mg-containing apatite crystal and the result of Mg content analysis. This means that the ionic composition of the reaction solution can be adjusted to adjust the composition of the synthesized powder.

FIGS. 7 and 8 show the results of electron microscope and XRD measurement of apatite in examples. As a result of phase analysis of the powder synthesized by varying the pulse width (pulse width) and power of the laser, a pure hydroxyapatite (hydroxyapatite) phase was observed under all laser conditions. This means that the powder can be stably synthesized without causing a phase change even if the laser conditions (pulse width and power) are changed.

Fig. 9 shows that pure hydroxyapatite, apatite having a Mg component, and powder having a whitlockite (whitlockite) phase can be synthesized by adjusting the components of the precursor solution.

Fig. 10 is a result of EDS measured after apatite was generated according to an example. The ratio of the component contents of Ca and P of the synthesized powder when the powder was synthesized using the component-adjusted apatite-forming precursor solution is shown, showing that the powder whose Ca/P ratio was adjusted can be synthesized.

Fig. 11 is a result showing a change in crystallinity of the synthesized powder according to laser power when synthesizing the apatite powder using the laser. Fig. 11 (a) is an XRD measurement result of the apatite powder, and the higher the crystallinity, the thinner the thickness of the peak (peak), and the higher the height. At a laser power of 1W, a relatively high crystallinity is exhibited. FIG. 11 (b) is a result of observing the apatite powder by SEM, TEM, and TEM-SAD. The higher the crystallinity, the more white dots appear in TEM-SAD, and the relatively higher the crystallinity is shown at a laser power of 1W.

Fig. 12 is a result showing the variation of crystallinity of the synthesized powder according to the laser pulse width when synthesizing the apatite powder using the laser. Referring to fig. 12, the crystallinity is relatively high at a pulse width of the laser of 4ns, and relatively low at 200 ns.

Summarizing the results of fig. 11 and 12, the power and pulse width of the laser can be varied to adjust the crystallinity of the synthesized apatite powder.

In summary, according to the embodiments of the present invention, it is possible to form a apatite film while forming apatite powder particles, and therefore, the powder preparation method is simple, and it is possible to manufacture products of various sizes and shapes by subsequent powder molding, and therefore, the utilization rate is high.

The present invention has been described with reference to preferred embodiments, but the present invention is not limited to the embodiments, and those skilled in the art can make various changes and modifications within the scope not departing from the spirit of the present invention. Such variations and modifications are to be considered within the purview and scope of the invention and the claims appended hereto.

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