CN101862630B - Preparation method of hydroxyapatite hollow microsphere in core/shell composite structure - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 16
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004005 microsphere Substances 0.000 title abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 55
- 239000011575 calcium Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 3
- 238000004140 cleaning Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000037452 priming Effects 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 43
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 42
- 238000003760 magnetic stirring Methods 0.000 abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 abstract description 5
- 230000002431 foraging effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 208000004434 Calcinosis Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- MEQOSCYFKJPQKH-UHFFFAOYSA-N calcium lithium borate Chemical compound [Li+].[Ca+2].[O-]B([O-])[O-] MEQOSCYFKJPQKH-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Abstract
本发明公开了一种核/壳复合结构羟基磷灰石空心微球的制备方法，按照以下步骤实施：对SiO2-Al2O3空心微球碱热处理：用蒸馏水超声波清洗SiO2-Al2O3空心微球，采用碱液体系对空心微球表面进行活化处理，再经去离子水清洗数次洗去残留在空心微球表面的碱液；空心微球表面沉积羟基磷灰石：在磁力搅拌下，向Ca(OH)2悬浮液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入H3PO4溶液；或者向Ca(NO)3-4H2O溶液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入(NH4)2HPO4溶液，同时采用氨水调节pH值，静置陈化后用酒精清洗，晾干；煅烧处理，即成。本发明方法制备的HA空心微球结晶度高、球形度好。The invention discloses a preparation method of hydroxyapatite hollow microspheres with a core/shell composite structure, which is carried out according to the following steps: Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres: ultrasonic cleaning of SiO 2 -Al 2 with distilled water O 3 hollow microspheres, use lye system to activate the surface of the hollow microspheres, and then wash several times with deionized water to wash away the lye remaining on the surface of the hollow microspheres; deposit hydroxyapatite on the surface of the hollow microspheres: Under magnetic stirring, add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(OH) 2 suspension, and then slowly add the H 3 PO 4 solution; or add the Ca(NO) 3 -4H 2 O Add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step into the solution, then slowly add the (NH 4 ) 2 HPO 4 solution, and adjust the pH value with ammonia water, let it stand for aging, wash it with alcohol, and dry it in the air; Calcination treatment, Serve. The HA hollow microspheres prepared by the method of the invention have high crystallinity and good sphericity.
Description
技术领域 technical field
本发明属于复合材料制备技术领域，涉及一种核/壳复合结构的羟基磷灰石空心微球的制备方法。 The invention belongs to the technical field of composite material preparation, and relates to a preparation method of hydroxyapatite hollow microspheres with a core/shell composite structure.
背景技术 Background technique
SiO2-Al2O3空心微球具有形状规则、密度小、抗压强度高、分散性好等优异性能，且通过一些先进技术对其进行表面改性处理可得到具有特殊性能的新材料而成为近几年的研究热点。 SiO 2 -Al 2 O 3 hollow microspheres have excellent properties such as regular shape, low density, high compressive strength, and good dispersibility, and new materials with special properties can be obtained through surface modification with some advanced technologies. become a research hotspot in recent years.
作为最有代表性的生物活性陶瓷材料，羟基磷灰石（Ca10(PO)6(OH)2, 以下简称HA）在近代生物医学领域一直受到人们的密切关注，尤其是具有密度小、比表面积大、及宽阔内部空隙等特点的HA空心微球，被认为是一种潜在的药物载体、抗菌材料载体及细胞培养微载体材料等。 As the most representative bioactive ceramic material, hydroxyapatite (Ca 10 (PO) 6 (OH) 2 , hereinafter referred to as HA) has been paid close attention to in the field of modern biomedicine, especially for its low density, specific HA hollow microspheres with large surface area and wide internal voids are considered to be a potential drug carrier, antibacterial material carrier and cell culture microcarrier material.
目前，有关HA空心微球的制备方法有很多，同济大学的黄文旵、Aihua Yao等人采用火焰漂浮法制备锂钙硼酸盐(LCB)玻璃微球，然后依此为模板在表面沉积磷酸钙盐，将LCB全部溶蚀后，壳层600℃煅烧处理4 h得到HA空心微球。山东大学吕宇鹏等人采用等离子体熔融法制备了HA空心微球，该法具体步骤为将一定粒度的HA颗粒等离子熔融后喷入低温介质中制备得到的。此外，还有人提出利用喷雾干燥法制备HA空心微球，该法具体步骤为向HA料浆中加入添加剂后进行喷雾干燥，得到由HA纳米晶粒构成的HA空心微球。上述方法中都获得了不同粒径、不同性能的HA空心微球，但是这些制备方法对空心微球制品的密度、形貌、直径等方面的限制比较多，尤其是对空心微球的类型及规格要求较高，一定程度上制约了制备HA空心微球的推广。 At present, there are many methods for preparing HA hollow microspheres. Huang Wenzhen, Aihua Yao and others from Tongji University used the flame floating method to prepare lithium calcium borate (LCB) glass microspheres, and then used this as a template to deposit calcium phosphate on the surface. , after all the LCB was dissolved, the shell was calcined at 600 °C for 4 h to obtain HA hollow microspheres. Lu Yupeng of Shandong University and others prepared HA hollow microspheres by plasma melting method. The specific steps of this method are to spray HA particles with a certain particle size into a low-temperature medium after plasma melting. In addition, some people proposed to prepare HA hollow microspheres by spray drying method. The specific steps of this method are to add additives to HA slurry and then spray dry to obtain HA hollow microspheres composed of HA nanocrystals. The above methods have obtained HA hollow microspheres with different particle sizes and different properties, but these preparation methods have many restrictions on the density, shape, diameter, etc. of the hollow microspheres, especially the type and size of the hollow microspheres The specification requirements are relatively high, which to some extent restricts the promotion of the preparation of HA hollow microspheres.
发明内容 Contents of the invention
本发明的目的是提供一种核/壳复合结构的羟基磷灰石空心微球的制备方法，该方法不受SiO2-Al2O3空心微球制品的密度、形貌、直径的限制，得到的核/壳复合结构的HA空心微球的结晶度高、球形度好。 The purpose of the present invention is to provide a method for preparing hydroxyapatite hollow microspheres with a core/shell composite structure, which is not limited by the density, shape and diameter of SiO 2 -Al 2 O 3 hollow microspheres. The obtained HA hollow microspheres with core/shell composite structure have high crystallinity and good sphericity.
本发明采用的技术方案是，一种核/壳复合结构的羟基磷灰石空心微球的制备方法，按照以下步骤实施： The technical scheme adopted in the present invention is, a method for preparing hollow hydroxyapatite microspheres with a core/shell composite structure, which is implemented according to the following steps:
步骤1、对SiO2-Al2O3空心微球碱热处理： Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres:
用蒸馏水超声波清洗SiO2-Al2O3空心微球；采用碱液体系对SiO2-Al2O3空心微球表面进行活化处理，在200-400转/分钟的磁力搅拌速度下活化反应3-8h，再经去离子水清洗数次洗去残留在空心微球表面的碱液； Ultrasonic cleaning of SiO 2 -Al 2 O 3 hollow microspheres with distilled water; use lye system to activate the surface of SiO 2 -Al 2 O 3 hollow microspheres, and activate the reaction at a magnetic stirring speed of 200-400 rpm 3 -8h, then washed several times with deionized water to remove the lye remaining on the surface of the hollow microspheres;
步骤2、空心微球表面沉积羟基磷灰石： Step 2, deposition of hydroxyapatite on the surface of hollow microspheres:
在200-400转/分钟的磁力搅拌速度下，向Ca(OH)2悬浮液中加入步骤1处理好的SiO2-Al2O3空心微球，然后缓慢加入H3PO4溶液，Ca(OH)2悬浮液浓度为0.3-0.8mol/L，H3PO4浓度为0.2-0.5 mol/L； At a magnetic stirring speed of 200-400 rpm, add the SiO 2 -Al 2 O 3 hollow microspheres treated in step 1 to the Ca(OH) 2 suspension, then slowly add the H 3 PO 4 solution, Ca( OH) 2 suspension concentration is 0.3-0.8mol/L, H 3 PO 4 concentration is 0.2-0.5 mol/L;
或者在200-400转/分钟的磁力搅拌速度下，向Ca(NO)3-4H2O溶液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入 (NH4)2HPO4溶液，Ca(NO)3-4H2O浓度为0.5-1.0mol/L，(NH4)2HPO4浓度为0.3-0.6mol/L， Or add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(NO) 3 -4H 2 O solution at a magnetic stirring speed of 200-400 rpm, and then slowly add (NH 4 ) 2 HPO 4 solution, the concentration of Ca(NO) 3 -4H 2 O is 0.5-1.0mol/L, the concentration of (NH 4 ) 2 HPO 4 is 0.3-0.6mol/L,
上述反应过程中采用氨水调节pH值介于10-14之间，反应温度控制在60-90℃，静置陈化时间不大于24h，后用酒精清洗，晾干； In the above reaction process, ammonia water is used to adjust the pH value between 10-14, the reaction temperature is controlled at 60-90°C, the standing aging time is not more than 24h, and then cleaned with alcohol and dried in the air;
步骤3、煅烧处理：将步骤2所制备的空心微球进行煅烧处理，煅烧温度为600-900℃，保温0.5-3h，即获得具有核/壳复合结构的HA空心微球。 Step 3, calcining treatment: calcining the hollow microspheres prepared in step 2 at a temperature of 600-900° C. and keeping them warm for 0.5-3 hours to obtain HA hollow microspheres with a core/shell composite structure.
本发明的核/壳复合结构的羟基磷灰石空心微球的制备方法，能够针对各种规格的SiO2-Al2O3空心微球，操作简单，所制备的羟基磷灰石空心微球的结晶度高、球形度好，适合工业化生产。 The preparation method of hydroxyapatite hollow microspheres with core/shell composite structure of the present invention can be aimed at SiO 2 -Al 2 O 3 hollow microspheres of various specifications, and the operation is simple, and the prepared hydroxyapatite hollow microspheres It has high crystallinity and good sphericity, and is suitable for industrial production.
具体实施方式 Detailed ways
下面结合具体实施方式对本发明进行详细说明。 The present invention will be described in detail below in combination with specific embodiments.
本发明的核/壳复合结构羟基磷灰石空心微球的制备方法，按照以下步骤具体实施： The preparation method of the core/shell composite structure hydroxyapatite hollow microspheres of the present invention is specifically implemented according to the following steps:
步骤1、对SiO2-Al2O3空心微球碱热处理： Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres:
用蒸馏水超声波清洗SiO2-Al2O3空心微球；采用碱液体系对SiO2-Al2O3空心微球表面进行活化处理，在200-400转/分钟的磁力搅拌速度下活化反应3-8h，再经去离子水清洗数次洗去残留在空心微球表面的碱液。 Ultrasonic cleaning of SiO 2 -Al 2 O 3 hollow microspheres with distilled water; use lye system to activate the surface of SiO 2 -Al 2 O 3 hollow microspheres, and activate the reaction at a magnetic stirring speed of 200-400 rpm 3 -8h, and then washed several times with deionized water to remove the lye remaining on the surface of the hollow microspheres.
碱液体系优选氢氧化钙(Ca(OH)2)-水(H2O)或氢氧化钠(NaOH)-水(H2O)体系，碱液浓度为0.5-1.0mol/L，碱液温度为60-90℃，选用氢氧化钙(钠)： SiO2-Al2O3空心微球的质量配比为1：1-5。 The lye system is preferably calcium hydroxide (Ca(OH) 2 )-water (H 2 O) or sodium hydroxide (NaOH)-water (H 2 O) system, the lye concentration is 0.5-1.0mol/L, the lye The temperature is 60-90°C, and the mass ratio of calcium hydroxide (sodium):SiO 2 -Al 2 O 3 hollow microspheres is 1:1-5.
步骤2、空心微球表面沉积HA： Step 2, depositing HA on the surface of hollow microspheres:
采用两种方式之一在空心微球表面沉积HA，一种方式是以Ca(OH)2与H3PO4为原料，另一种方式是以Ca(NO)3-4H2O与(NH4)2HPO4为原料。 HA was deposited on the surface of hollow microspheres in one of two ways, one way is to use Ca(OH) 2 and H 3 PO 4 as raw materials, and the other way is to use Ca(NO) 3 -4H 2 O and (NH 4 ) 2 HPO 4 as starting material.
即在200-400转/分钟的磁力搅拌速度下，向Ca(OH)2悬浮液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入H3PO4溶液，Ca(OH)2悬浮液浓度为0.3-0.8mol/L，H3PO4浓度为0.2-0.5 mol/L，反应过程中采用氨水(NH3-H2O)调节pH值介于10-14之间。 That is, at the magnetic stirring speed of 200-400 rpm, add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(OH) 2 suspension, and then slowly add the H 3 PO 4 solution, Ca The concentration of (OH) 2 suspension is 0.3-0.8mol/L, the concentration of H 3 PO 4 is 0.2-0.5 mol/L, and ammonia water (NH 3 -H 2 O) is used to adjust the pH value between 10-14 during the reaction between.
或者在200-400转/分钟的磁力搅拌速度下，向Ca(NO)3-4H2O溶液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入 (NH4)2HPO4溶液，Ca(NO)3-4H2O浓度为0.5-1.0mol/L，(NH4)2HPO4浓度为0.3-0.6mol/L，反应过程中采用氨水调节pH值介于10-14之间。 Or add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(NO) 3 -4H 2 O solution at a magnetic stirring speed of 200-400 rpm, and then slowly add (NH 4 ) 2 HPO 4 solution, the concentration of Ca(NO) 3 -4H 2 O is 0.5-1.0mol/L, and the concentration of (NH 4 ) 2 HPO 4 is 0.3-0.6mol/L. During the reaction, ammonia water is used to adjust the pH value between 10 Between -14.
本步骤过程中，反应温度控制在60-90℃，静置陈化时间不大于24h，后用酒精清洗，晾干。 During this step, the reaction temperature is controlled at 60-90° C., and the standing aging time is not more than 24 hours, and then cleaned with alcohol and dried in the air.
步骤3、煅烧处理： Step 3, calcining treatment:
将步骤2所制备的空心微球进行煅烧处理，煅烧温度为600-900℃，保温0.5-3h，即获得结晶度高、球形度好的核壳复合结构HA空心微球。 The hollow microspheres prepared in step 2 are calcined at a temperature of 600-900° C. and kept for 0.5-3 hours to obtain HA hollow microspheres with a core-shell composite structure with high crystallinity and good sphericity.
本发明的方法，以SiO2-Al2O3空心微球为核，在表面沉积羟基磷灰石，制备既具有前者理想的球形结构及低密度，又兼有良好后者生物相容性的核壳复合结构空心微球。 The method of the present invention uses SiO 2 -Al 2 O 3 hollow microspheres as the core, deposits hydroxyapatite on the surface, and prepares the hydroxyapatite which not only has the ideal spherical structure and low density of the former, but also has good biocompatibility of the latter. Hollow microspheres with core-shell composite structure.
实施例1 Example 1
步骤1、对SiO2-Al2O3空心微球碱热处理：用蒸馏水超声波清洗SiO2-Al2O3空心微球20min；采用氢氧化钙(Ca(OH)2)-水(H2O)对SiO2-Al2O3空心微球表面进行活化处理，碱液浓度为0.5mol/L，碱液温度为80℃，氢氧化钙与SiO2-Al2O3空心微球的质量比为1：5；在200转/分钟的磁力搅拌速度下活化反应4h，再经去离子水清洗数次洗去残留在空心微球表面的碱液。 Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres: ultrasonically clean SiO 2 -Al 2 O 3 hollow microspheres with distilled water for 20 min; use calcium hydroxide (Ca(OH) 2 )-water (H 2 O ) Activate the surface of SiO 2 -Al 2 O 3 hollow microspheres, the concentration of alkali solution is 0.5mol/L, the temperature of alkali solution is 80°C, the mass ratio of calcium hydroxide to SiO 2 -Al 2 O 3 hollow microspheres The ratio is 1:5; activate the reaction for 4 hours at a magnetic stirring speed of 200 rpm, and then wash with deionized water several times to remove the lye remaining on the surface of the hollow microspheres.
步骤2、空心微球表面沉积HA：即在200转/分钟的磁力搅拌速度下，向Ca(OH)2悬浮液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入H3PO4溶液，Ca(OH)2悬浮液浓度为0.5mol/L，H3PO4浓度为0.25 mol/L，反应过程中采用氨水调节pH值介于11-12之间，反应温度控制在80℃，静置陈化时间24h，后用酒精清洗，晾干。 Step 2. Deposit HA on the surface of the hollow microspheres: add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(OH) 2 suspension at a magnetic stirring speed of 200 rpm, and then slowly Add H 3 PO 4 solution, Ca(OH) 2 suspension concentration is 0.5mol/L, H 3 PO 4 concentration is 0.25 mol/L, use ammonia water to adjust the pH value between 11-12 during the reaction, the reaction temperature Control it at 80°C, let it stand for 24 hours, and then wash it with alcohol and dry it in the air.
步骤3、煅烧处理：将步骤2所制备的空心微球进行煅烧处理，煅烧温度为600℃，保温0.5h，即成。 Step 3, calcining treatment: calcining the hollow microspheres prepared in step 2, the calcining temperature is 600° C., and the temperature is kept for 0.5 h, and it is ready.
实施例2 Example 2
步骤1、对SiO2-Al2O3空心微球碱热处理：用蒸馏水超声波清洗SiO2-Al2O3空心微球；采用氢氧化钠(NaOH)-水(H2O)体系，对SiO2-Al2O3空心微球表面进行活化处理，碱液浓度为0.6mol/L，碱液温度为90℃，氢氧化钠与 SiO2-Al2O3空心微球的质量配比为1：4；在300转/分钟的磁力搅拌速度下活化反应8h，再经去离子水清洗数次洗去残留在空心微球表面的碱液。 Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres: Ultrasonic cleaning of SiO 2 -Al 2 O 3 hollow microspheres with distilled water; The surface of 2 -Al 2 O 3 hollow microspheres is activated, the concentration of alkali solution is 0.6mol/L, the temperature of alkali solution is 90°C, and the mass ratio of sodium hydroxide to SiO 2 -Al 2 O 3 hollow microspheres is 1 : 4; Activate the reaction for 8 hours at a magnetic stirring speed of 300 rpm, and then wash with deionized water several times to remove the lye remaining on the surface of the hollow microspheres.
步骤2、空心微球表面沉积HA：即在300转/分钟的磁力搅拌速度下，向Ca(OH)2悬浮液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入H3PO4溶液，Ca(OH)2悬浮液浓度为0.8mol/L，H3PO4浓度为0.2mol/L，反应过程中采用氨水调节pH值介于12-13之间，反应温度控制在90℃，静置陈化时间20h，后用酒精清洗，晾干。 Step 2. Deposit HA on the surface of the hollow microspheres: add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(OH) 2 suspension at a magnetic stirring speed of 300 rpm, and then slowly Add H 3 PO 4 solution, the concentration of Ca(OH) 2 suspension is 0.8mol/L, and the concentration of H 3 PO 4 is 0.2mol/L. During the reaction, ammonia water is used to adjust the pH value between 12-13, and the reaction temperature Control it at 90°C, let it stand for 20 hours, and then wash it with alcohol and dry it in the air.
步骤3、煅烧处理：将步骤2所制备的空心微球进行煅烧处理，煅烧温度为700℃，保温1h，即成。 Step 3, calcining treatment: calcining the hollow microspheres prepared in step 2 at a calcination temperature of 700° C. and keeping it warm for 1 hour.
实施例3 Example 3
步骤1、对SiO2-Al2O3空心微球碱热处理：用蒸馏水超声波清洗SiO2-Al2O3空心微球；采用氢氧化钙(Ca(OH)2)-水(H2O)体系，对SiO2-Al2O3空心微球表面进行活化处理，碱液浓度为1.0mol/L，碱液温度为60℃，氢氧化钙与 SiO2-Al2O3空心微球的质量比为1：3；在400转/分钟的磁力搅拌速度下活化反应3h，再经去离子水清洗数次洗去残留在空心微球表面的碱液。 Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres: ultrasonically clean SiO 2 -Al 2 O 3 hollow microspheres with distilled water; use calcium hydroxide (Ca(OH) 2 )-water (H 2 O) system, activate the surface of SiO 2 -Al 2 O 3 hollow microspheres, the concentration of alkali solution is 1.0mol/L, the temperature of alkali solution is 60℃, the mass of calcium hydroxide and SiO 2 -Al 2 O 3 hollow microspheres The ratio is 1:3; activate the reaction for 3 hours at a magnetic stirring speed of 400 rpm, and then wash with deionized water several times to remove the lye remaining on the surface of the hollow microspheres.
步骤2、空心微球表面沉积HA：在400转/分钟的磁力搅拌速度下，向Ca(NO)3-4H2O溶液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入 (NH4)2HPO4溶液，Ca(NO)3-4H2O浓度为1.0mol/L，(NH4)2HPO4浓度为0.6mol/L，反应过程中采用氨水调节pH值介于13-14之间，反应温度控制在60℃，静置陈化时间22h，后用酒精清洗，晾干。 Step 2, depositing HA on the surface of the hollow microspheres: at a magnetic stirring speed of 400 rpm, add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(NO) 3 -4H 2 O solution, Then slowly add (NH 4 ) 2 HPO 4 solution, the concentration of Ca(NO) 3 -4H 2 O is 1.0mol/L, and the concentration of (NH 4 ) 2 HPO 4 is 0.6mol/L. During the reaction, use ammonia water to adjust the pH value Between 13-14, the reaction temperature is controlled at 60°C, and the aging time is 22 hours, then cleaned with alcohol and dried in the air.
步骤3、煅烧处理：将步骤2所制备的空心微球进行煅烧处理，煅烧温度为800℃，保温3h，即成。 Step 3, calcining treatment: calcining the hollow microspheres prepared in step 2 at a calcination temperature of 800° C. and keeping it warm for 3 hours.
实施例4 Example 4
步骤1、对SiO2-Al2O3空心微球碱热处理：用蒸馏水超声波清洗SiO2-Al2O3空心微球；采用氢氧化钠(NaOH)-水(H2O)体系，对SiO2-Al2O3空心微球表面进行活化处理，碱液浓度为0.8mol/L，碱液温度为70℃，氢氧化钠与SiO2-Al2O3空心微球的质量配比为1：1；在350转/分钟的磁力搅拌速度下活化反应6h，再经去离子水清洗数次洗去残留在空心微球表面的碱液。 Step 1. Alkaline heat treatment of SiO 2 -Al 2 O 3 hollow microspheres: Ultrasonic cleaning of SiO 2 -Al 2 O 3 hollow microspheres with distilled water; The surface of 2 -Al 2 O 3 hollow microspheres is activated, the concentration of lye is 0.8mol/L, the temperature of lye is 70°C, and the mass ratio of sodium hydroxide to SiO 2 -Al 2 O 3 hollow microspheres is 1 : 1; Activate the reaction for 6 hours at a magnetic stirring speed of 350 rpm, and then wash with deionized water several times to remove the lye remaining on the surface of the hollow microspheres.
步骤2、空心微球表面沉积HA：在350转/分钟的磁力搅拌速度下，向Ca(NO)3-4H2O溶液中加入上步处理好的SiO2-Al2O3空心微球，然后缓慢加入 (NH4)2HPO4溶液，Ca(NO)3-4H2O浓度为0.75mol/L，(NH4)2HPO4浓度为0.45mol/L，反应过程中采用氨水调节pH值介于10-11之间，反应温度控制在70℃，静置陈化时间20h，后用酒精清洗，晾干。 Step 2, depositing HA on the surface of the hollow microspheres: at a magnetic stirring speed of 350 rpm, add the SiO 2 -Al 2 O 3 hollow microspheres treated in the previous step to the Ca(NO) 3 -4H 2 O solution, Then slowly add (NH 4 ) 2 HPO 4 solution, the concentration of Ca(NO) 3 -4H 2 O is 0.75mol/L, the concentration of (NH 4 ) 2 HPO 4 is 0.45mol/L, and the pH value is adjusted by ammonia water during the reaction Between 10-11, the reaction temperature is controlled at 70°C, and the aging time is 20 hours, then cleaned with alcohol and dried in the air.
步骤3、煅烧处理：将步骤2所制备的空心微球进行煅烧处理，煅烧温度为900℃，保温2h，即成。 Step 3, calcining treatment: calcining the hollow microspheres prepared in step 2 at a calcination temperature of 900° C., and keeping it warm for 2 hours, and it is ready.
上述实施例得到的各个核/壳复合结构的羟基磷灰石空心微球制品，结晶度高、球形度好、密度低，符合使用技术要求。 The hydroxyapatite hollow microsphere products of each core/shell composite structure obtained in the above examples have high crystallinity, good sphericity, and low density, which meet the technical requirements for use.
本发明方法以SiO2-Al2O3空心微球为模板，采用碱热处理技术对SiO2-Al2O3空心微球进行表面活化处理，采用化学合成法在SiO2-Al2O3空心微球表面沉积HA，然后清洗过滤干燥后，获得以SiO2-Al2O3空心微球为核，HA为壳的核/壳复合结构空心微球，结晶度高、球形度好、密度低的核/壳复合结构HA空心微球，完全适应不同SiO2-Al2O3空心微球的表面处理要求。 The method of the present invention uses SiO 2 -Al 2 O 3 hollow microspheres as a template, adopts alkali heat treatment technology to carry out surface activation treatment on SiO 2 -Al 2 O 3 hollow microspheres, and adopts chemical synthesis method in SiO 2 -Al 2 O 3 hollow microspheres Deposit HA on the surface of the microspheres, then wash, filter and dry to obtain hollow microspheres with a core/shell composite structure with SiO 2 -Al 2 O 3 hollow microspheres as the core and HA as the shell, with high crystallinity, good sphericity and low density The core/shell composite structure HA hollow microspheres fully adapt to the surface treatment requirements of different SiO 2 -Al 2 O 3 hollow microspheres.
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| CN1597610A (en) * | 2004-09-22 | 2005-03-23 | 山东大学 | Hydroxy apatite hollow microsphere and its preparation method |
| CN101343054A (en) * | 2008-08-19 | 2009-01-14 | 华南理工大学 | A kind of preparation method of hydroxyapatite microsphere |
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| US4328967A (en) * | 1979-12-26 | 1982-05-11 | Columbia Industries, Inc. | Lightweight bowling ball |
| CN1594201A (en) * | 2004-07-14 | 2005-03-16 | 天津大学 | Composite microsphere containing hydroxyapatite and preparing method thereof |
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