WO2018188338A1 - 一种在磷酸钙类生物陶瓷基体表面构建的白磷钙石涂层及其制备方法 - Google Patents

一种在磷酸钙类生物陶瓷基体表面构建的白磷钙石涂层及其制备方法 Download PDF

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WO2018188338A1
WO2018188338A1 PCT/CN2017/111794 CN2017111794W WO2018188338A1 WO 2018188338 A1 WO2018188338 A1 WO 2018188338A1 CN 2017111794 W CN2017111794 W CN 2017111794W WO 2018188338 A1 WO2018188338 A1 WO 2018188338A1
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calcium phosphate
bioceramic
substrate
coating
sample
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French (fr)
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王迎军
郭晓恒
赵娜如
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/327—After-treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5048—Phosphates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the invention belongs to the field of preparation of biomedical materials, and in particular relates to a white pahophosphestite coating constructed on the surface of a calcium phosphate bioceramic substrate and a preparation method thereof.
  • Paphagite (Ca 18 Mg 2 (HPO 4 ) 2 (PO 4 ) 12 ) is a calcium phosphate mineral mainly found in biological bones and teeth. It is the second most inorganic mineral in biological bones, only second. In hydroxyapatite.
  • a white calcium phosite powder is prepared from a cationic aqueous solution.
  • Calcium phosphate bioactive ceramics have good biocompatibility, osteoconductivity, osteoinductivity and biodegradability, and are widely used in the field of biological bone repair. Since the structure of calcium phosphate has a certain similarity with the picocalcite, the picocalcite increases the structure of the calcium phosphate (HPO 4 ) 2- and Mg 2+ , so that the white palygorous coating material is constructed on the surface of the calcium phosphate. Become a new surface coating construction method.
  • the invention is based on the similarity between the structure of the calcium phosphate ceramic and the pico-calcite ceramic, and proposes a preparation method for constructing the coating of the pico-calcium phosphate on the surface of the calcium phosphate ceramic, effectively realizing the preparation of the coating of the white pa Precisely control the crystal morphology and size of the pico-alumina coating.
  • the object of the present invention is to overcome the problems of the prior art, and to provide a coating of a white magnesia stone on the surface of a calcium phosphate bioceramic substrate and a preparation method thereof.
  • the method can regulate the morphology and size of the pico-alumina coated crystal.
  • the present invention adopts the following technical solutions.
  • the object of the present invention is achieved by the following scheme.
  • a method for constructing a coating of a white magnesia on a surface of a calcium phosphate bioceramic substrate comprising the steps of:
  • the calcium phosphate bioceramic substrate obtained in the step (1) is placed in a solution containing Mg2+ , and then transferred to a high temperature and high pressure reactor. Hydrothermal;
  • step (2) The sample after the hydrothermal reaction is taken out from the reaction vessel, washed, dried, and the surface of the sample is coated with a wollastonite.
  • the method for preparing the pure calcium phosphate-based bioceramic powder in the step (1) is a chemical precipitation method, a hydrothermal method, a sol-gel method, a solid phase reaction method, an alcohol compound method or a precursor method.
  • the calcium phosphate bioceramic described in the step (1) is at least one of calcium phosphate bioceramics such as tricalcium phosphate ( ⁇ -type, ⁇ -type), hydroxyapatite, tetracalcium phosphate, and dicalcium phosphate.
  • calcium phosphate bioceramics such as tricalcium phosphate ( ⁇ -type, ⁇ -type), hydroxyapatite, tetracalcium phosphate, and dicalcium phosphate.
  • the calcination temperature of the calcination in the step (1) is 700-900 ° C, and the holding time is 2-4 h.
  • the method of forming in the step (1) is dry press molding, isostatic pressing, plastic molding, slip casting or extrusion molding.
  • the calcination temperature of the calcination in the step (1) is 900-1100 ° C, and the holding time is 2-4 h.
  • the Mg 2+ -containing solution in the step (2) is a soluble Mg 2+ -containing aqueous solution such as a simulated body fluid (SBF), a Mg 2+ -containing phosphate buffer solution, a magnesium chloride solution or a magnesium nitrate solution.
  • a soluble Mg 2+ -containing aqueous solution such as a simulated body fluid (SBF), a Mg 2+ -containing phosphate buffer solution, a magnesium chloride solution or a magnesium nitrate solution.
  • the step (2) pH of the solution containing Mg 2+ is 5.4-7.4; bulk mass ratio of calcium phosphate bioceramics solution matrix containing Mg 2+ is 0.3-2.4 L / g; the The hydrothermal reaction temperature is 80-120 ° C and the time is 6 h -5 d.
  • the cleaning in the step (3) is to sequentially wash the sample with acetone and deionized water; the drying is performed by placing the sample in a drying oven at 40-50 ° C for drying.
  • a coating of a wollastonite prepared by the method of constructing a coating of a wollastonite on the surface of a calcium phosphate-based bioceramic substrate as described above.
  • the present invention has the following advantages:
  • the method for constructing a coating of a picro-calcite coating on the surface of a calcium phosphate bioceramic substrate effectively solves the preparation of a pure white palygorskite coating, and at the same time well regulates the crystal morphology and crystal of the coating of the pico-calcium coating. Dimensions are of great significance for expanding the use of biomedical materials.
  • Figure 1 is an X-ray diffraction (XRD) pattern of a coating of a wollastonite in Example 1 of the present invention.
  • Example 2 is a field emission scanning electron microscope (SEM) image of a wollastonite coating in Example 1 of the present invention.
  • Figure 3 is a field emission scanning electron microscope (SEM) image of a white magnesia coating in Example 2 of the present invention.
  • Example 4 is a field emission scanning electron microscope (SEM) image of a white magnesia coating in Example 3 of the present invention.
  • the mixture is continuously stirred for 12 hours, and then the precipitate is washed three times with deionized water, and the precipitate is transferred to an oven at 80 ° C to be dried, thereby preparing a pure calcium phosphate bioceramic powder. It is pre-fired, burned to 900 °C, and kept for 3 h. Then, the pre-treated calcium phosphate bioceramic powder is shaped and dried, and 0.05 g of calcium phosphate bioceramic powder is put into the mold. Under the pressure of 1.0 MPa, hold the pressure for 2 min to obtain the calcium phosphate bioceramic substrate, which was calcined, burned to 1100 °C, and kept for 3 h.
  • SBF simulated body fluid
  • SBF simulated body fluid
  • Method preparation In 700 ml of deionized water were added 8.035 g NaCl, 0.355 g NaHCO 3 , 0.225 g KCl, 0.231 g K 2 HPO 4 • 3H 2 O, 0.311 g MgCl 2 • 6H 2 O, 1 M HCl solution 39 Ml , 0.292 g CaCl 2 , 0.072 g Na 2 SO 4 , keep stirring, wait until the sample is completely dissolved, add deionized water to 900 ml, add 0.618 g tris and 1 M HCl solution, and control the solution pH at 7.42-7.45 during the process.
  • the X-ray diffraction peak of the coating of the white magbergite coating corresponds to the standard card one by one, and the crystallinity is good and the strength is high, thereby indicating success.
  • a pure white patina coating is obtained.
  • the wollastonite coating prepared in this example has uniform morphology and uniform grain size, and exhibits a hexagonal plate-like morphology. Its field emission scanning electron microscope (SEM) is shown in Fig. 2.
  • the mixture is continuously stirred for 12 hours, and then the precipitate is washed three times with deionized water, and the precipitate is transferred to an oven at 80 ° C to be dried, thereby preparing a pure calcium phosphate bioceramic powder. It is pre-fired, burned to 800 ° C, and kept for 2 h. Then, the pre-treated calcium phosphate bioceramic powder is shaped and dried, that is, 0.20 g of calcium phosphate bioceramic powder is put into the mold.
  • the volume-mass ratio of SBF to calcium phosphate bioceramic substrate was controlled to be 0.6 L/g, and the reaction time was 2 d.
  • the reacted sample was taken out from the reaction vessel, washed successively with acetone and deionized water, and the sample was placed in a drying oven at 40 ° C for drying treatment, and the surface of the sample was coated with a wollastonite.
  • the wollastonite coating prepared in this example has uniform morphology and uniform grain size, and exhibits a three-sided plate-like morphology. Its field emission scanning electron microscope (SEM) image is shown in Fig. 3.
  • the mixture is continuously stirred for 12 h, then the precipitate is washed three times with deionized water, and the precipitate is transferred to an oven at 80 ° C to be dried, thereby preparing a pure calcium phosphate bioceramic powder.
  • the pre-treated calcium phosphate bioceramic powder is shaped, using dry pressing, that is, 0.15 g of calcium phosphate bioceramic powder into the mold In the pressure of 2.0 MPa, the pressure is maintained for 2 min to obtain the calcium phosphate bioceramic substrate, which is calcined, burned to 900 ° C, and the holding time is 4 h; the sample is placed in a simulated body fluid (SBF) with a pH of 7.4.
  • SBF simulated body fluid

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Abstract

在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法及得到的涂层，制备方法包括以下步骤：先制备出纯净的磷酸钙类生物陶瓷粉末，然后将纯净的磷酸钙类生物陶瓷粉末预烧、成型、煅烧，得磷酸钙类生物陶瓷基体，将其置于含Mg 2+的溶液中，再转移至高温高压反应釜中进行水热反应，后清洗、干燥，得到白磷钙石涂层。

Description

一种在磷酸钙类生物陶瓷基体表面构建的白磷钙石涂层及其制备方法
技术领域
本发明属于生物医用材料制备领域，尤其涉及一种在磷酸钙类生物陶瓷基体表面构建的白磷钙石涂层及其制备方法。
背景技术
白磷钙石（ Ca18Mg2(HPO4)2(PO 4)12 ）是一种磷酸钙类矿物，主要存在于生物骨与牙齿中，是生物骨中含量第二多的无机矿物，仅次于羟基磷灰石。
目前，关于白磷钙石的研究并不是很多，一方面由于其在体内存在周期较短，并且检测比较困难，另一方面是现阶段合成高纯度的白磷钙石相对比较困难。有研究者利用 CaCl2 、 MgCl2 和 Na2HPO4 作为原料，在 100℃ 的条件下进行反应制备白磷钙石，也有研究者将 Ca2+ 和 Mg2+ 逐滴加入磷酸盐的水溶液中制备白磷钙石，但是这两种方法制备出来的白磷钙石均有杂质相的生成，难以合成纯净的白磷钙石。当然，随着科研人员对白磷钙石的认识逐渐加深，其制备方法也有了新的突破， Ki 等人利用 Ca(OH)2-Mg(OH)2-H3PO 4 三元系统，在过量 Mg2+ 和 pH=4.2 的条件下，合成了纯净的白磷钙石；也有 CN 1035699855 A 的专利利用含 Ca 离子和除 Ca 离子以外其他阳离子溶液为原料，加入磷酸，之后老化包括磷酸供给材料的阳离子水溶液制备白磷钙石粉末。这两种方法在一定程度上突破了关于白磷钙石粉末的合成，但是由于其复杂的操作条件与精准的实验要求，使得合成过程变得困难。另外，关于高纯的白磷钙石涂层的制备方法不曾报道。
磷酸钙类生物活性陶瓷，具有良好的生物相容性、骨传导性、骨诱导性、生物降解性，被广泛用于生物骨修复领域。由于磷酸钙的结构与白磷钙石具有一定的相似性，白磷钙石是在磷酸钙的结构上增加了 (HPO4)2- 与 Mg2+ ，使得在磷酸钙表面构建白磷钙石涂层材料成为一种新型表面涂层构建方法。本发明基于磷酸钙陶瓷与白磷钙石陶瓷结构上的相似性，提出一种在磷酸钙陶瓷表面构建白磷钙石涂层的制备方法，有效的实现了关于白磷钙石涂层的制备，同时实现了精确调控白磷钙石涂层晶体形貌与尺寸大小。
发明内容
本发明的目的在于克服现有相关技术存在的问题，提供一种在磷酸钙类生物陶瓷基体表面构建的白磷钙石涂层及其制备方法。该方法能调控白磷钙石涂层晶体的形貌与尺寸大小。
为实现上述目的，本发明采用如下的技术方案。
本发明的目的通过下述方案实现。
一种在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法，包括以下步骤：
（ 1 ）磷酸钙类生物陶瓷基体的制备：先制备出纯净的磷酸钙类生物陶瓷粉末，然后将纯净的磷酸钙类生物陶瓷粉末预烧、成型、煅烧，得磷酸钙类生物陶瓷基体；
（ 2 ）在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层：将步骤（ 1 ）所得的磷酸钙类生物陶瓷基体置于含 Mg2+ 的溶液中，再转移至高温高压反应釜中进行水热反应；
（ 3 ）对样品的后处理：将步骤（ 2 ）水热反应后的样品从反应釜中取出来，清洗，干燥，样品表面得白磷钙石涂层。
优选的，步骤（1）中制备纯净的磷酸钙类生物陶瓷粉末的方法为化学沉淀法、水热法、溶胶凝胶法、固相反应法、醇化合物法或前驱体法。
优选的，步骤（1）所述的磷酸钙生物陶瓷为磷酸三钙（α型、β型）、羟基磷灰石、磷酸四钙和磷酸二钙等钙磷类生物陶瓷中的一种以上。
优选的，步骤（1）所述预烧的烧成温度为700-900℃，保温时间为2-4 h。
优选的，步骤（1）所述成型的方法为干压成型、等静压成型、可塑成型、注浆成型或挤出成型。
优选的，步骤（1）所述煅烧的烧成温度为900-1100℃，保温时间为2-4 h。
优选的，步骤（ 2 ）所述含 Mg2+ 的溶液为模拟体液（ SBF ）、含 Mg2+ 的磷酸盐缓冲液、氯化镁溶液或硝酸镁溶液等可溶性含 Mg2+ 的水溶液。
优选的，步骤（ 2 ）所述含 Mg2+ 的溶液的 pH 为 5.4-7.4 ；所述含 Mg2+ 的溶液与磷酸钙类生物陶瓷基体的体积质量比为 0.3-2.4 L/g ；所述水热反应的温度为 80-120 ℃ ，时间为 6 h-5 d 。
优选的，步骤（3）所述清洗是将样品依次用丙酮与去离子水进行洗涤；所述的干燥为将样品置于40-50℃的干燥烘箱中进行干燥。
由以上所述的一种在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法制备的白磷钙石涂层。
与现有技术相比，本发明具有如下优点：
本发明在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法有效的解决了关于纯净的白磷钙石涂层的制备，同时很好的调控了白磷钙石涂层的晶体形貌与晶体尺寸大小，对于拓展生物医用材料的应用有重大的推动意义。
附图说明
图1为本发明实施例1中白磷钙石涂层的X射线衍射（XRD）图。
图2为本发明实施例1中白磷钙石涂层的场发射扫描电子显微镜（SEM）图。
图3为本发明实施例2中白磷钙石涂层的场发射扫描电子显微镜（SEM）图。
图4为本发明实施例3中白磷钙石涂层的场发射扫描电子显微镜（SEM）图。
具体实施方式
为了更好的理解本发明，下面结合实施例对本发明作进一步说明，但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例 1
利用化学沉淀法，按照 Ca/P 摩尔比为 1.5 称取 21.2535 gCa(NO3)2•4H2O 与 (NH4)2HPO4 于 A 、 B 两个烧杯中， 分别加入去离子水充分溶解，用体积比为 1:1 的氨水调节 B 杯缓冲液 pH 值为 9.0 ，将 B 杯的溶液逐滴加入 A 杯中，并且不断搅拌，同时利用体积比为 1:1 的氨水控制滴加过程中的 pH 值为 6.8 ，滴加完毕后，连续搅拌 12 h ，随后用去离子水洗涤沉淀 3 次，将沉淀转入 80 ℃的烘箱中烘干，从而 制备出纯净的磷酸钙生物陶瓷粉末，将其进行预烧处理，烧至 900 ℃ ，保温时间 3 h ，随后将预处理后的磷酸钙生物陶瓷粉末进行成型处理，采用干压成型 ，即将 0.05 g 的磷酸钙生物陶瓷粉末装入模具中，在 1.0 MPa 的压力下，保压 2 min ，得到 磷酸钙生物陶瓷基体，将其进行煅烧处理， 烧至 1100 ℃ ，保温时间为 3 h ；将样品置于 pH 为 7.4 的 模拟体液（ SBF ）中， 其中 SBF 按照以下方法配制：在 700 ml 去离子水中依次加入 8.035 g NaCl ， 0.355 g NaHCO3 ， 0.225 g KCl ， 0.231 g K2HPO4•3H2O ， 0.311 g MgCl2•6H2O ， 1 M 的 HCl 溶液 39 ml ， 0.292 g CaCl2 ， 0.072 g Na2SO4, 不断搅拌，待样品完全溶解，加去离子水至 900 ml ，加入 0.618 g tris 和 1 M 的 HCl 溶液，过程中控制溶液 pH 在 7.42-7.45 ，至 tris 加完，调节 pH 为 7.4 ， 加去离子水至 1000 ml ，整个过程控制温度为 36.5 ℃ 。 随后 转移至高温高压的反应釜中，在 120 ℃ 的条件下进行水热反应， 控制 SBF 与 磷酸钙生物陶瓷基体的体积质量比为 2.4 L/g ，反应时间为 4 d ，将水热反应后的样品从反应釜中取出来， 依次用丙酮与去离子水进行洗涤处理， 将 样品置于 45 ℃ 的干燥烘箱中进行干燥处理，样品表面得白磷钙石涂层。 本实施例所得的白磷钙石涂层的 X 射线衍射（ XRD ）见图 1 ，白磷钙石涂层的 X 射线衍射峰与标准卡片一一对应，结晶性良好，强度较高，由此表明成功制得纯净白磷钙石涂层 。 本实施 例 制备的白磷钙石涂层的形貌一致、晶粒尺寸大小均一，表现为六边板状形貌，它的场发射扫描电子显微镜（ SEM ）图见图 2 。
实施例 2
利用化学沉淀法，按照 Ca/P 摩尔比为 1.5 称取 21.2535 g Ca(NO3)2•4H2O 与 (NH4)2HPO4 于 A 、 B 两个烧杯中， 加入去离子水充分溶解，用体积比为 1:1 的氨水调节 B 杯缓冲液 pH 值为 9.0 ，将 B 杯的溶液逐滴加入 A 杯中，并且不断搅拌，同时利用体积比为 1:1 的氨水控制滴加过程中的 pH 值为 6.8 ，滴加完毕后，连续搅拌 12 h ，随后用去离子水洗涤沉淀 3 次，将沉淀转入 80 ℃的烘箱中烘干，从而 制备出纯净的磷酸钙生物陶瓷粉末，将其进行预烧处理，烧至 800℃ ，保温时间 2 h ，随后将预处理后的磷酸钙生物陶瓷粉末进行成型处理，采用干压成型 ，即将 0.20 g 的磷酸钙生物陶瓷粉末装入模具中，在 2.0 MPa 的压力下，保压 3 min ，得到 磷酸钙生物陶瓷基体，将其进行煅烧处理， 烧至 1000℃ ，保温时间为 2 h ；将样品置于 pH 为 7.4 的 模拟体液（ SBF ）中，其中 SBF 按照以下方法配制： 在 700 ml 去离子水中依次加入 8.035 g NaCl ， 0.355 g NaHCO3 ， 0.225 g KCl ， 0.231 g K2HPO4•3H2O ， 0.311 g MgCl2•6H2O ， 1 M 的 HCl 溶液 39 ml ， 0.292 g CaCl2 ， 0.072 g Na2SO4, 不断搅拌，待样品完全溶解，加去离子水至 900 ml ，加入 0.618 g tris 和 1 M 的 HCl 溶液，过程中控制溶液 pH 在 7.42-7.45 ，至 tris 加完，调节 pH 为 7.4 ，加去离子水至 1000 ml ，整个过程控制温度为 36.5 ℃ 。 随后 将其 转移至高温高压的反应釜中，在 120℃ 的条件下进行水热反应， 控制 SBF 与 磷酸钙生物陶瓷基体的体积质量比为 0.6 L/g ， 反应时间为 2 d ，将水热反应后的样品从反应釜中取出来， 依次用丙酮与去离子水进行洗涤处理， 将 将样品置于 40℃ 的干燥烘箱中进行干燥处理，样品表面得白磷钙石涂层。本实施 例 制备的白磷钙石涂层的形貌一致、晶粒尺寸大小均一，表现为三边板状形貌，它的场发射扫描电子显微镜（ SEM ）图见图 3 。
实施例 3
首先利用化学沉淀法，按照 Ca/P 摩尔比为 1.5 称取 21.2535 g Ca(NO3)2•4H2O 与 (NH4)2HPO4 于 A 、 B 两个烧杯中，加入去离子水充分溶解， 用体积比为 1:1 的氨水调节 B 杯缓冲液 pH 值为 9.0 ，将 B 杯的溶液逐滴加入 A 杯中，并且不断搅拌，同时利用体积比为 1:1 的氨水控制滴加过程中的 pH 值为 6.8 ，滴加完毕后，连续搅拌 12 h ，随后用去离子水洗涤沉淀 3 次，将沉淀转入 80 ℃的烘箱中烘干，从而 制备出纯净的磷酸钙生物陶瓷粉末，将其进行预烧处理，烧至 700℃ ，保温时间 4 h ，随后将预处理后的磷酸钙生物陶瓷粉末进行成型处理，采用干压成型 ，即将 0.15 g 的磷酸钙生物陶瓷粉末装入模具中，在 2.0 MPa 的压力下，保压 2 min ，得到 磷酸钙生物陶瓷基体，将其进行煅烧处理， 烧至 900℃ ，保温时间为 4 h ；将样品置于 pH 为 7.4 的 模拟体液（ SBF ）中，其中 SBF 按照以下方法配制： 在 700 ml 去离子水中依次加入 8.035 g NaCl ， 0.355 g NaHCO3 ， 0.225 g KCl ， 0.231 g K2HPO4•3H2O ， 0.311 g MgCl2•6H2O ， 1 M 的 HCl 溶液 39 ml ， 0.292 g CaCl2 ， 0.072 g Na2SO4, 不断搅拌， 待样品完全溶解，加去离子水至 900 ml ，加入 0.618 g tris 和 1 M 的 HCl 溶液，过程中控制溶液 pH 在 7.42-7.45 ，至 tris 加完，调节 pH 为 7.4 ，加去离子水至 1000 ml ，整个过程控制温度为 36.5 ℃ 。 随后 将其 转移至高温高压的反应釜中，在 80℃ 的条件下进行水热反应， 控制 SBF 与 磷酸钙生物陶瓷基体的体积质量比为 0.3 L/g ， 反应时间为 5 d ，将水热反应后的样品从反应釜中取出来， 依次用丙酮与去离子水进行洗涤处理， 将 样品置于 50℃ 的干燥烘箱中进行干燥处理，样品表面得白磷钙石涂层。本实施 例 制备的白磷钙石涂层的形貌一致、晶粒尺寸大小均一，表现为球状形貌，它的场发射扫描电子显微镜（ SEM ）图见图 4 。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所做的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法，其特征在于，包括以下步骤：
    （ 1 ）磷酸钙类生物陶瓷基体的制备：先制备出纯净的磷酸钙类生物陶瓷粉末，然后将纯净的磷酸钙类生物陶瓷粉末预烧、成型、煅烧，得磷酸钙类生物陶瓷基体；
    （ 2 ）在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层：将步骤（ 1 ）所得的磷酸钙类生物陶瓷基体置于含 Mg2+ 的溶液中，再转移至高温高压反应釜中进行水热反应；
    （ 3 ）对样品的后处理：将步骤（ 2 ）水热反应后的样品从反应釜中取出来，清洗，干燥，样品表面得白磷钙石涂层。
  2. 根据权利要求1所述的方法，其特征在于，步骤（1）中制备纯净的磷酸钙类生物陶瓷粉末的方法为化学沉淀法、水热法、溶胶凝胶法、固相反应法、醇化合物法或前驱体法。
  3. 根据权利要求1所述的方法，其特征在于，步骤（1）所述的磷酸钙生物陶瓷为磷酸三钙、羟基磷灰石、磷酸四钙和磷酸二钙中的一种以上。
  4. 根据权利要求1所述的方法，其特征在于，步骤（1）所述预烧的烧成温度为700-900℃，保温时间为2-4 h。
  5. 根据权利要求1所述的方法，其特征在于，步骤（1）所述成型的方法为干压成型、等静压成型、可塑成型、注浆成型或挤出成型。
  6. 根据权利要求1所述的方法，其特征在于，步骤（1）所述煅烧的烧成温度为900-1100℃，保温时间为2-4 h。
  7. 根据权利要求1所述的方法，其特征在于，所述含Mg2+的溶液为SBF模拟体液、含Mg2+的磷酸盐缓冲液、氯化镁溶液或硝酸镁溶液。
  8. 根据权利要求1所述的方法，其特征在于，步骤（2）所述含Mg2+的溶液的pH为5.4-7.4；所述含Mg2+的溶液与磷酸钙类生物陶瓷基体的体积质量比为0.3-2.4 L/g；所述水热反应的温度为80-120℃，时间为6 h-5 d。
  9. 根据权利要求1所述的方法，其特征在于，步骤（3）所述清洗是将样品依次用丙酮与去离子水进行洗涤；所述的干燥为将样品置于40-50℃的干燥烘箱中进行干燥。
  10. 由权利要求1-9任一项所述的一种在磷酸钙类生物陶瓷基体表面构建白磷钙石涂层的方法制备的白磷钙石涂层。
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