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CN110240137A - A kind of preparation method of nano hydroxyapatite powder - Google Patents

A kind of preparation method of nano hydroxyapatite powder Download PDF

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Publication number
CN110240137A
CN110240137A CN201910328004.5A CN201910328004A CN110240137A CN 110240137 A CN110240137 A CN 110240137A CN 201910328004 A CN201910328004 A CN 201910328004A CN 110240137 A CN110240137 A CN 110240137A
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Prior art keywords
hydroxyapatite powder
preparation
nano hydroxyapatite
nano
ionic calcium
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王欣宇
张博文
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Priority to CN201910328004.5A priority Critical patent/CN110240137A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/32Phosphates of magnesium, calcium, strontium, or barium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/10Particle morphology extending in one dimension, e.g. needle-like
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/10Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Materials For Medical Uses (AREA)
  • Medicinal Preparation (AREA)

Abstract

The present invention provides a kind of preparation method of nano hydroxyapatite powder, 1) preparation method is the following steps are included: configure phosphate anion solution, and adjust the pH value of the phosphate anion solution to 10-12;2) ionic calcium soln is configured, and adjusts the pH value of the ionic calcium soln to 10-12;3) it is placed in the phosphate anion solution of ultrasound environments after being atomized the ionic calcium soln by ullrasonic spraying with certain flow rate penetrating, then, stands, obtain precipitation of hydroxyapatite;4) precipitation of hydroxyapatite is washed, then, freeze-drying obtains nano hydroxyapatite powder.The present invention synthesizes that partial size is small and uniform hydroxyapatite nano-powder using supersonic spraying combination conventional ultrasound method in higher concentration and under room temperature.

Description

A kind of preparation method of nano hydroxyapatite powder
Technical field
The present invention relates to nano-powder preparation technical field, in particular to a kind of preparation side of nano hydroxyapatite powder Method.
Background technique
Hydroxyapatite (HAP) is the highest inorganic constituent of content in skeleton, this kind of material has good Bioactivity and biocompatibility, HAP bioceramic can be a kind of energy with the very strong chemical combination key of bon e formation after being implanted into human body Enough excellent materials to substitute skeleton, and there is good bone conduction effect, play the role of inducing new bone growth.But The mechanical property of hydroxylapatite ceramic is bad, and lower mechanical strength is the key that restrict it to play a role in terms of bone repair Point.Studies have shown that the Some Mechanical Properties of the HAP ceramics of synthesis have improvement when hydroxyapatite powder reaches nanoscale.Cause This, the preparation of nano-HAP powder is present main direction of studying.
The method for preparing nanometer hydroxyapatite is broadly divided into dry method (solid reaction process) and wet process (solution reaction method).By It is larger in the hydroxy apatite powder partial size that dry process goes out, and since long-time mix grinding raw material causes raw material easy to be dirty Dye, and wet method equipment demand is simple, and obtained diameter of particle is small and uniform, therefore generally use wet process.Wet process has: hydro-thermal Method, chemical precipitation method, microemulsion method, sol-gel method etc..Due to wanting industrialized production nanometer hydroxyapatite, need to control Cost, it is easy to operate, therefore this prior synthesizing method of chemical precipitation method is widely used.Chemical precipitation method is to prepare nano-HAP The conventional method of powder has required experiment condition lower, and the process of reaction is easily controlled, the very low advantage of cost, the party Method is that phosphorus source and calcium source are mixed stirring, then adjusts pH with ammonium hydroxide, and then generates HAP precipitating, then by standing, washing It washs, after drying and other steps, by powder calcination, so that HAP crystal is obtained, but the nano-hydroxy-apatite that chemical precipitation method is prepared For stone powder reuniting situation than more serious, uniformity is poor.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method of nano hydroxyapatite powder, to solve existing hydroxyl The problem of base apatite powder partial size is big, particle diameter distribution is uneven and preparation process is easy to appear reunion.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of nano hydroxyapatite powder, comprising the following steps:
1) phosphate anion solution is prepared, and adjusts the pH value of the phosphate anion solution to 10-12;
2) ionic calcium soln is prepared, and adjusts the pH value of the ionic calcium soln to 10-12;
3) it is placed in described in ultrasound environments after being atomized the ionic calcium soln by ullrasonic spraying with certain flow rate penetrating In phosphate anion solution, then, stands, obtain precipitation of hydroxyapatite;
4) precipitation of hydroxyapatite is washed, then, freeze-drying obtains nano hydroxyapatite powder.
Optionally, the concentration of phosphate anion solution described in the step 1) is 0.12mol/L-0.3mol/L, and institute The calcium-phosphorus ratio for stating ionic calcium soln described in phosphate anion solution and the step 2) is 1.67.
Optionally, the step 1) and solution used in adjusting pH value in the step 2) are concentrated ammonia liquor.
Optionally, the ullrasonic spraying nebulisation time of ionic calcium soln described in the step 3) is 5min-20min.
Optionally, flow velocity described in the step 3) is 2ml/min-8ml/min.
Optionally, nano hydroxyapatite powder described in the step 4) be needle-shaped and corynebacterium, and it is described it is needle-shaped and It is 60-120nm that the nano hydroxyapatite powder of corynebacterium, which obtains length,.
Optionally, the average grain diameter of nano hydroxyapatite powder described in the step 4) is 70-90nm.
Compared with the existing technology, the preparation method of nano hydroxyapatite powder of the present invention has the advantage that
1, the preparation method of nano hydroxyapatite powder of the invention first uses the method for ullrasonic spraying by reaction solution Become liquid droplet, increased considerably the contact area of reactant, so as to dramatically increase nucleation density, promote nucleus It is formed and is grown, while there is the mist drop of large energy to also play positive facilitation to the nucleation of HAP phase and growth, It recycles conventional ultrasound to synthesize nanometer hydroxyapatite, by ultrasonic cavitation, improves the energy of synthetic environment, and by Cause strong stirring action in the whirling motion of cavitation bubble, eliminate local non-uniform phenomenon, controls the synchronous growth of nucleus, together When, cavitation also substantially reduces the specific surface energy of nucleus, it is suppressed that the aggregation of nucleus with grow up, and also due to crush make With precipitating has been smashed, the uniformity of the nano hydroxyapatite powder of synthesis is improved, reunion is improved.
2, the present invention substantially reduces the entire reaction time of synthesis nano hydroxyapatite powder, reduces higher concentration Under agglomeration traits, and crystallinity is also promoted.
3, the preparation process of nano hydroxyapatite powder of the present invention is simple, easy to operate, whole process reaction condition temperature With do not need high temperature high pressure process.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is 50k times of Scanning Electron microscope (SEM) of nano hydroxyapatite powder prepared by the embodiment of the present invention 1 Photo;
Fig. 2 is 100k times of Scanning Electron microscope (SEM) of nano hydroxyapatite powder prepared by the embodiment of the present invention 2 Photo;
Fig. 3 is 100k times of Scanning Electron microscope (SEM) of nano hydroxyapatite powder prepared by the embodiment of the present invention 3 Photo.
Specific embodiment
It is to accelerate and control chemical reaction by ultrasonic cavitation energy that ultrasonic method, which prepares nano-powder, promotes the yield of reaction The new chemical reaction with initiation, wherein conventional ultrasound method is that ultrasonic wave is propagated around by liquid medium, is reaching certain energy When, ultrasonic cavitation can occur for liquid medium, accelerate heat transfer and mass transport process between interface, improve the synthesis speed of chemical reaction Rate and yield.
Supersonic spraying is to be converted one of solution to one surely by ultrasonic cavitation energy by ultrasonication The misty liquid droplets of amount are sprayed into another reaction solution and are synthesized, due to misty liquid droplets have the characteristics that uniformly it is tiny, and have There is energy, therefore may synthesize and obtain uniformly tiny nano-powder, which is from inlet when ultrasonic wave through being transmitted to Up to liquid outlet solution surface when, liquid-gas interface ie in solution surface and air interface are in be surpassed by perpendicular to interface After the effect of sound wave, due to the effect of ultrasonic wave, solution surface is made to form tensile wave, with the enhancing of surface tension wave energy, When surface tension wave energy reaches certain value, also increase the liquid made at its wave crest simultaneously in the tensile wave wave crest of solution surface Droplet flies out.
The present invention is based on this, is synthesized using supersonic spraying combination conventional ultrasound method in higher concentration and under room temperature Partial size is small and uniform hydroxyapatite nano-powder.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase Mutually combination.
Below in conjunction with drawings and examples, the present invention will be described in detail.
Embodiment 1
A kind of preparation method of nano hydroxyapatite powder, comprising the following steps:
1) the phosphate anion solution that 160ml concentration is 0.12mol/L is prepared, and phosphate anion is adjusted using concentrated ammonia liquor The pH value of solution is to 10;
2) ionic calcium soln that 40ml concentration is 0.2004mol/L is prepared, and ionic calcium soln is adjusted using concentrated ammonia liquor PH value is to 10;
3) phosphoric acid for being placed in ultrasound environments is sprayed into after being atomized ionic calcium soln by ullrasonic spraying with the flow velocity of 2ml/min In radical ion solution, wherein the ullrasonic spraying nebulisation time of ionic calcium soln is 20min, has been sprayed into whole ionic calcium solns Mixed solution is stood half an hour, obtains precipitation of hydroxyapatite by Bi Hou;
4) precipitation of hydroxyapatite is poured into centrifuge tube, repeatedly washing is using ultrapure water and dehydrated alcohol and by centrifugation Neutrality, then by after the precipitation of hydroxyapatite freezing for 24 hours of washes clean, be placed in freeze drier dry 12h, obtain white Nano hydroxyapatite powder.
Embodiment 2
A kind of preparation method of nano hydroxyapatite powder, comprising the following steps:
1) the phosphate anion solution that configuration 160ml concentration is 0.12mol/L, and phosphate anion is adjusted using concentrated ammonia liquor The pH value of solution is to 10;
2) ionic calcium soln that configuration 40ml concentration is 0.2004mol/L, and ionic calcium soln is adjusted using concentrated ammonia liquor PH value is to 10;
3) phosphoric acid for being placed in ultrasound environments is sprayed into after being atomized ionic calcium soln by ullrasonic spraying with the flow velocity of 8ml/min In radical ion solution, wherein the ullrasonic spraying nebulisation time of ionic calcium soln is 5min, is finished to the penetrating of whole ionic calcium solns Afterwards, mixed solution is stood into half an hour, obtains precipitation of hydroxyapatite;
4) precipitation of hydroxyapatite is poured into centrifuge tube, repeatedly washing is using ultrapure water and dehydrated alcohol and by centrifugation Neutrality, then by after the precipitation of hydroxyapatite freezing for 24 hours of washes clean, be placed in freeze drier dry 12h, obtain white Nano hydroxyapatite powder.
Embodiment 3
A kind of preparation method of nano hydroxyapatite powder, comprising the following steps:
1) the phosphate anion solution that configuration 160ml concentration is 0.3mol/L, and phosphate anion is adjusted using concentrated ammonia liquor The pH value of solution is to 10;
2) ionic calcium soln that configuration 40ml concentration is 0.501mol/L, and using the pH of concentrated ammonia liquor adjusting ionic calcium soln It is worth to 10;
3) phosphoric acid for being placed in ultrasound environments is sprayed into after being atomized ionic calcium soln by ullrasonic spraying with the flow velocity of 8ml/min In radical ion solution, wherein the ullrasonic spraying nebulisation time of ionic calcium soln is 5min, is finished to the penetrating of whole ionic calcium solns Afterwards, mixed solution is stood into half an hour, obtains precipitation of hydroxyapatite;
4) precipitation of hydroxyapatite is poured into centrifuge tube, repeatedly washing is using ultrapure water and dehydrated alcohol and by centrifugation Neutrality, then by after the precipitation of hydroxyapatite freezing for 24 hours of washes clean, be placed in freeze drier dry 12h, obtain white Nano hydroxyapatite powder.
Pattern test carried out to the nano hydroxyapatite powder of 1~embodiment of embodiment 3, test result respectively as Fig. 1, Shown in Fig. 2 and Fig. 3.
By Fig. 1, Fig. 2 and Fig. 3 it is found that the nano hydroxyapatite powder of 1~embodiment of the embodiment of the present invention 3 be it is needle-shaped and Corynebacterium, and the length of needle-shaped and corynebacterium nano hydroxyapatite powder is 60-120nm.
The fineness of the nano hydroxyapatite powder of 1~embodiment of embodiment 3 is tested.
After tested it is found that the average grain diameter of the nano hydroxyapatite powder of 1~embodiment of the embodiment of the present invention 3 is 70- 90nm。
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of nano hydroxyapatite powder, which comprises the following steps:
1) phosphate anion solution is prepared, and adjusts the pH value of the phosphate anion solution to 10-12;
2) ionic calcium soln is prepared, and adjusts the pH value of the ionic calcium soln to 10-12;
3) phosphoric acid for being placed in ultrasound environments is sprayed into after being atomized the ionic calcium soln by ullrasonic spraying with certain flow rate In radical ion solution, then, stands, obtain precipitation of hydroxyapatite;
4) precipitation of hydroxyapatite is washed, then, freeze-drying obtains nano hydroxyapatite powder.
2. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that in the step 1) The concentration of the phosphate anion solution is 0.12mol/L-0.3mol/L, and the phosphate anion solution and the step 2) Described in ionic calcium soln calcium-phosphorus ratio be 1.67.
3. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that the step 1) and It is concentrated ammonia liquor that solution used in pH value is adjusted in the step 2).
4. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that in the step 3) The ullrasonic spraying nebulisation time of the ionic calcium soln is 5min-20min.
5. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that in the step 3) The flow velocity is 2ml/min-8ml/min.
6. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that in the step 4) The nano hydroxyapatite powder is needle-shaped and corynebacterium, and described needle-shaped and corynebacterium nano hydroxyapatite powder obtains Length is 60-120nm.
7. the preparation method of nano hydroxyapatite powder according to claim 1, which is characterized in that in the step 4) The average grain diameter of the nano hydroxyapatite powder is 70-90nm.
CN201910328004.5A 2019-04-22 2019-04-22 A kind of preparation method of nano hydroxyapatite powder Pending CN110240137A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112195026A (en) * 2020-10-14 2021-01-08 武汉理工大学 Europium-doped beta-tricalcium phosphate fluorescent nano-particles and preparation method and application thereof
CN112978695A (en) * 2021-03-16 2021-06-18 华东理工大学 Preparation method of bionic hydroxyapatite nanoparticles with high osteogenic activity

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544318A (en) * 2003-11-21 2004-11-10 陕西科技大学 Nanometer hydroxyapatite powder preparation method
RU2342938C1 (en) * 2007-08-14 2009-01-10 Государственное образовательное учреждение высшего профессионального образования "Белгородский государственный университет" Method of obtaining nano-sized hydroxylapatite
CN101343056A (en) * 2008-07-30 2009-01-14 宁波大学 Method for preparing hydroxyapatite nano-powder
CN102424581A (en) * 2011-09-15 2012-04-25 广州倍绣生物技术有限公司 Hydroxyapatite biological ceramic for bone connection and bone repair and preparation method thereof
CN103071447A (en) * 2013-02-05 2013-05-01 东华大学 Method for preparing strontium-doped hydroxyapatite through supersound
CN103241719A (en) * 2013-04-25 2013-08-14 太原理工大学 Preparation method of high-orientation nanometer hydroxyapatite crystalline colloidal array
CN103553012A (en) * 2013-11-07 2014-02-05 中山大学 Method for preparing nano hydroxyapatite

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544318A (en) * 2003-11-21 2004-11-10 陕西科技大学 Nanometer hydroxyapatite powder preparation method
RU2342938C1 (en) * 2007-08-14 2009-01-10 Государственное образовательное учреждение высшего профессионального образования "Белгородский государственный университет" Method of obtaining nano-sized hydroxylapatite
CN101343056A (en) * 2008-07-30 2009-01-14 宁波大学 Method for preparing hydroxyapatite nano-powder
CN102424581A (en) * 2011-09-15 2012-04-25 广州倍绣生物技术有限公司 Hydroxyapatite biological ceramic for bone connection and bone repair and preparation method thereof
CN103071447A (en) * 2013-02-05 2013-05-01 东华大学 Method for preparing strontium-doped hydroxyapatite through supersound
CN103241719A (en) * 2013-04-25 2013-08-14 太原理工大学 Preparation method of high-orientation nanometer hydroxyapatite crystalline colloidal array
CN103553012A (en) * 2013-11-07 2014-02-05 中山大学 Method for preparing nano hydroxyapatite

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112195026A (en) * 2020-10-14 2021-01-08 武汉理工大学 Europium-doped beta-tricalcium phosphate fluorescent nano-particles and preparation method and application thereof
CN112195026B (en) * 2020-10-14 2022-12-23 武汉理工大学 Europium-doped beta-tricalcium phosphate fluorescent nano-particles and preparation method and application thereof
CN112978695A (en) * 2021-03-16 2021-06-18 华东理工大学 Preparation method of bionic hydroxyapatite nanoparticles with high osteogenic activity

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