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CN104803673A - A kind of hydroxyapatite/sodium titanate composite bioceramics and its preparation method - Google Patents

A kind of hydroxyapatite/sodium titanate composite bioceramics and its preparation method Download PDF

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CN104803673A
CN104803673A CN201510146843.7A CN201510146843A CN104803673A CN 104803673 A CN104803673 A CN 104803673A CN 201510146843 A CN201510146843 A CN 201510146843A CN 104803673 A CN104803673 A CN 104803673A
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hydroxyapatite
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sodium titanate
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nano
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CN104803673B (en
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潘林根
刘乐峰
郭玉芹
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Foshan Sanshui High-Power Inorganic Material Co Ltd
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Suzhou Vivotide Biotechnologies Co ltd
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Abstract

The invention discloses a hydroxyapatite/sodium titanate composite bioceramic and a preparation method thereof, relates to the field of biological materials, and is prepared from the following components in parts by mass: 30-50 parts of hydroxyapatite, 20-40 parts of sodium titanate, 5-10 parts of nano titanium oxide, 3-7 parts of zirconium oxide, 2-6 parts of boron nitride, 5-10 parts of aluminum oxide and 2-5 parts of nano zinc oxide. A preparation method of hydroxyapatite/sodium titanate composite bioceramic comprises the following preparation steps: weighing; (2) ball milling; (3) cold press molding; (4) high-temperature calcination; (5) and (6) cooling. The hydroxyapatite/sodium titanate composite biological ceramic provided by the invention further improves the biological performance of the hydroxyapatite by utilizing the promoting effect of the sodium titanate on the biological activity of the hydroxyapatite. Therefore, the hydroxyapatite/sodium titanate composite bioceramic provided by the invention has better bioactivity and is an ideal bone repair substitute material.

Description

一种羟基磷灰石/钛酸钠复合生物陶瓷及其制备方法A kind of hydroxyapatite/sodium titanate composite bioceramics and its preparation method

技术领域 technical field

本发明属于生物材料领域，特别涉及一种羟基磷灰石/钛酸钠复合生物陶瓷及该生物陶瓷的制备方法。 The invention belongs to the field of biological materials, in particular to a hydroxyapatite/sodium titanate composite bioceramic and a preparation method of the bioceramic.

背景技术 Background technique

随着材料科技的发展，生物材料因其对机体组织进行修复、替代与再生的特殊性能，已经成为当今生物医学领域重要的研究方向之一。生物硬组织代用材料最早是使用体骨、动物骨，后来发展到采用不锈钢和塑料，由于不锈钢存在溶析、腐蚀和疲劳问题，塑料存在稳定性差和强度低的问题。因此造成生物材料发展的瓶颈，生物陶瓷的出现，改善了现有替代材料的不足，因其诸多优势，因此，生物陶瓷具有了广阔的发展前景。 With the development of material science and technology, biomaterials have become one of the important research directions in the field of biomedicine because of their special properties of repairing, replacing and regenerating body tissues. Biological hard tissue substitute materials were first used body bones and animal bones, and later developed to use stainless steel and plastics. Due to the problems of dissolution, corrosion and fatigue of stainless steel, plastics have problems of poor stability and low strength. Therefore, the bottleneck in the development of biomaterials is caused. The emergence of bioceramics has improved the shortage of existing alternative materials. Because of its many advantages, bioceramics has broad development prospects.

磷酸钙陶瓷(CPC)是生物活性陶瓷材料中的重要种类，目前研究和应用最多的是羟基磷灰石(HA)和磷酸三钙(TCP)。磷酸钙陶瓷含有CaO和P2O5两种成份，是构成人体硬组织的重要无机物质，植入人体后，其表面同人体组织可通过键的结合，达到完全亲和。其中，HA在组成和结构上与人骨和牙齿非常相似，HA能使骨细胞附着在其表面, 随着新骨的生长，这个连接地带逐渐萎缩，并且HA通过晶体外层成为骨的一部分, 新骨可以从HA 植入体与原骨结合处沿着植入体表面或内部贯通性孔隙攀附生长。HA生物活性陶瓷是典型生物活性陶瓷，植入体内后能与组织在界面上形成化学键性结合,具有较高的力学性能，在人体生理环境中可溶解性较低。 Calcium phosphate ceramics (CPC) are an important type of bioactive ceramic materials, and currently the most researched and applied are hydroxyapatite (HA) and tricalcium phosphate (TCP). Calcium phosphate ceramics contain two components, CaO and P 2 O 5 , which are important inorganic substances that constitute the hard tissue of the human body. After being implanted in the human body, its surface can be bonded with human tissue to achieve complete affinity. Among them, HA is very similar to human bone and teeth in composition and structure, and HA can make bone cells attach to its surface. With the growth of new bone, this connecting zone gradually shrinks, and HA becomes a part of bone through the outer layer of the crystal, new Bone can grow from the joint between HA implant and original bone along the implant surface or internal penetrating pores. HA bioactive ceramics are typical bioactive ceramics, which can form chemical bonds with tissues on the interface after implantation, have high mechanical properties, and have low solubility in the human physiological environment.

目前，人们对钛酸钠的研究相对较少，钛酸钠也是具备一定生物活性的物质之一，其在陶瓷领域已经有所发展，已有研究表明，钛酸钠对羟基磷灰石的生物活性具有促进作用。 At present, there are relatively few studies on sodium titanate. Sodium titanate is also one of the substances with certain biological activity. Activity is facilitated.

发明内容 Contents of the invention

本发明解决的技术问题：针对上述不足，克服现有技术的缺陷，本发明的目的是提供一种羟基磷灰石/钛酸钠复合生物陶瓷及其制备方法。 The technical problem solved by the present invention: aiming at the above-mentioned deficiencies and overcoming the defects of the prior art, the purpose of the present invention is to provide a hydroxyapatite/sodium titanate composite bioceramic and its preparation method.

本发明的技术方案：一种羟基磷灰石/钛酸钠复合生物陶瓷，由以下质量份数的各个组分制备而成： Technical solution of the present invention: a hydroxyapatite/sodium titanate composite bioceramic prepared from the following components in parts by mass:

羟基磷灰石30-50份、钛酸钠20-40份、纳米氧化钛5-10份、氧化锆3-7份、氮化硼2-6份、氧化铝5-10份和纳米氧化锌2-5份。 30-50 parts of hydroxyapatite, 20-40 parts of sodium titanate, 5-10 parts of nano-titanium oxide, 3-7 parts of zirconia, 2-6 parts of boron nitride, 5-10 parts of aluminum oxide and nano-zinc oxide 2-5 servings.

作为优选，各个组分的质量份数为：羟基磷灰石35-45份、钛酸钠25-36份、纳米氧化钛6-9份、氧化锆4-6份、氮化硼3-5份、氧化铝6-8份和纳米氧化锌3-4份。 Preferably, the mass parts of each component are: 35-45 parts of hydroxyapatite, 25-36 parts of sodium titanate, 6-9 parts of nano-titanium oxide, 4-6 parts of zirconia, 3-5 parts of boron nitride parts, 6-8 parts of aluminum oxide and 3-4 parts of nano zinc oxide.

作为优选，各个组分的质量份数为：羟基磷灰石42份、钛酸钠34份、纳米氧化钛8份、氧化锆5份、氮化硼4份、氧化铝7份和纳米氧化锌3份。 Preferably, the mass parts of each component are: 42 parts of hydroxyapatite, 34 parts of sodium titanate, 8 parts of nano-titanium oxide, 5 parts of zirconia, 4 parts of boron nitride, 7 parts of aluminum oxide and nano-zinc oxide 3 copies.

一种羟基磷灰石/钛酸钠复合生物陶瓷的制备方法，制备步骤如下： A preparation method of hydroxyapatite/sodium titanate composite bioceramics, the preparation steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体进行冷压成型； (3) Cold-press forming: cold-press forming the mixed powder;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1000℃-1400℃，压力300-800MPa，时间3-10h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1000°C-1400°C, a pressure of 300-800MPa, and a time of 3-10h;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

作为优选，步骤（4）中煅烧的温度为1150℃。 Preferably, the calcining temperature in step (4) is 1150°C.

作为优选，步骤（4）中煅烧的压力为600MPa。 Preferably, the calcining pressure in step (4) is 600MPa.

有益效果：本发明提供的羟基磷灰石/钛酸钠复合生物陶瓷，是利用钛酸钠对羟基磷灰石生物活性的促进作用，进一步提高羟基磷灰石的生物性能。钛酸钠和羟基磷灰石经高温煅烧之后，钛酸钠形态发生变化，在钛酸钠层之中含有钙离子，含有钙离子的钛酸钠层对羟基磷灰石的沉积具有更高的诱惑力，在人体内更加促进羟基磷灰石的形成。 Beneficial effects: the hydroxyapatite/sodium titanate composite bioceramic provided by the present invention utilizes the promotion effect of sodium titanate on the biological activity of hydroxyapatite to further improve the biological performance of hydroxyapatite. After sodium titanate and hydroxyapatite are calcined at high temperature, the morphology of sodium titanate changes, and calcium ions are contained in the sodium titanate layer, and the sodium titanate layer containing calcium ions has a higher effect on the deposition of hydroxyapatite. Temptation, promotes the formation of hydroxyapatite in the human body.

因此，本发明提供的羟基磷灰石/钛酸钠复合生物陶瓷具有较好的生物活性，是一种理想的骨骼修复替代材料。 Therefore, the hydroxyapatite/sodium titanate composite bioceramic provided by the present invention has better biological activity and is an ideal substitute material for bone repair.

具体实施方式 Detailed ways

为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解， 这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。 In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with the examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

实施例 1： Example 1:

一种羟基磷灰石/钛酸钠复合生物陶瓷，包括以下质量份数的各个组分： A hydroxyapatite/sodium titanate composite bioceramic, comprising the following components in parts by mass:

羟基磷灰石50份、钛酸钠40份、纳米氧化钛10份、氧化锆7份、氮化硼6份、氧化铝10份和纳米氧化锌5份。 50 parts of hydroxyapatite, 40 parts of sodium titanate, 10 parts of nano-titanium oxide, 7 parts of zirconia, 6 parts of boron nitride, 10 parts of aluminum oxide and 5 parts of nano-zinc oxide.

根据本发明提供的制备方法制备羟基磷灰石/钛酸钠复合生物陶瓷，步骤如下： Prepare hydroxyapatite/sodium titanate composite bioceramics according to the preparation method provided by the present invention, the steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体采用60T压机进行压制； (3) Cold press forming: the mixed powder is pressed with a 60T press;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1300℃，压力700MPa，时间4h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1300°C and a pressure of 700MPa for 4 hours;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

对得到的块状羟基磷灰石/钛酸钠复合生物陶瓷进行检测，检测生物陶瓷的性能：硬度840HV；压缩强度1100MPa；抗弯强度420MPa；韧性16MPa·m1/2。 The obtained massive hydroxyapatite/sodium titanate composite bioceramic was tested, and the properties of the bioceramic were tested: hardness 840HV; compressive strength 1100MPa; flexural strength 420MPa; toughness 16MPa·m 1/2 .

实施例 2： Example 2:

一种羟基磷灰石/钛酸钠复合生物陶瓷，包括以下质量份数的各个组分： A hydroxyapatite/sodium titanate composite bioceramic, comprising the following components in parts by mass:

羟基磷灰石30份、钛酸钠20份、纳米氧化钛5份、氧化锆3份、氮化硼2份、氧化铝5份和纳米氧化锌2份。 30 parts of hydroxyapatite, 20 parts of sodium titanate, 5 parts of nano-titanium oxide, 3 parts of zirconia, 2 parts of boron nitride, 5 parts of aluminum oxide and 2 parts of nano-zinc oxide.

根据本发明提供的制备方法制备羟基磷灰石/钛酸钠复合生物陶瓷，步骤如下： Prepare hydroxyapatite/sodium titanate composite bioceramics according to the preparation method provided by the present invention, the steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体采用60T压机进行压制； (3) Cold press forming: the mixed powder is pressed with a 60T press;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1300℃，压力700MPa，时间7h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1300°C and a pressure of 700MPa for 7 hours;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

对得到的块状羟基磷灰石/钛酸钠复合生物陶瓷进行检测，检测生物陶瓷的性能：硬度810HV；压缩强度1060MPa；抗弯强度400MPa；韧性14MPa·m1/2。 The obtained massive hydroxyapatite/sodium titanate composite bioceramic was tested, and the properties of the bioceramic were tested: hardness 810HV; compressive strength 1060MPa; flexural strength 400MPa; toughness 14MPa·m 1/2 .

实施例 3： Example 3:

一种羟基磷灰石/钛酸钠复合生物陶瓷，包括以下质量份数的各个组分： A hydroxyapatite/sodium titanate composite bioceramic, comprising the following components in parts by mass:

羟基磷灰石35份、钛酸钠25份、纳米氧化钛6份、氧化锆4份、氮化硼3份、氧化铝6份和纳米氧化锌3份。 35 parts of hydroxyapatite, 25 parts of sodium titanate, 6 parts of nano-titanium oxide, 4 parts of zirconia, 3 parts of boron nitride, 6 parts of aluminum oxide and 3 parts of nano-zinc oxide.

根据本发明提供的制备方法制备羟基磷灰石/钛酸钠复合生物陶瓷，步骤如下： Prepare hydroxyapatite/sodium titanate composite bioceramics according to the preparation method provided by the present invention, the steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体采用60T压机进行压制； (3) Cold press forming: the mixed powder is pressed with a 60T press;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1150℃，压力600MPa，时间6h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1150°C and a pressure of 600MPa for 6 hours;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

对得到的块状羟基磷灰石/钛酸钠复合生物陶瓷进行检测，检测生物陶瓷的性能：硬度810HV；压缩强度1060MPa；抗弯强度400MPa；韧性14MPa·m1/2。 The obtained massive hydroxyapatite/sodium titanate composite bioceramic was tested, and the properties of the bioceramic were tested: hardness 810HV; compressive strength 1060MPa; flexural strength 400MPa; toughness 14MPa·m 1/2 .

实施例4： Example 4:

一种羟基磷灰石/钛酸钠复合生物陶瓷，包括以下质量份数的各个组分： A hydroxyapatite/sodium titanate composite bioceramic, comprising the following components in parts by mass:

羟基磷灰石45份、钛酸钠36份、纳米氧化钛9份、氧化锆6份、氮化硼5份、氧化铝8份和纳米氧化锌4份。 45 parts of hydroxyapatite, 36 parts of sodium titanate, 9 parts of nano-titanium oxide, 6 parts of zirconia, 5 parts of boron nitride, 8 parts of aluminum oxide and 4 parts of nano-zinc oxide.

根据本发明提供的制备方法制备羟基磷灰石/钛酸钠复合生物陶瓷，步骤如下： Prepare hydroxyapatite/sodium titanate composite bioceramics according to the preparation method provided by the present invention, the steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体采用60T压机进行压制； (3) Cold press forming: the mixed powder is pressed with a 60T press;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1150℃，压力600MPa，时间6h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1150°C and a pressure of 600MPa for 6 hours;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

对得到的块状羟基磷灰石/钛酸钠复合生物陶瓷进行检测，检测生物陶瓷的性能：硬度820HV；压缩强度1080MPa；抗弯强度410MPa；韧性16MPa·m1/2。 The obtained massive hydroxyapatite/sodium titanate composite bioceramic was tested, and the properties of the bioceramic were tested: hardness 820HV; compressive strength 1080MPa; flexural strength 410MPa; toughness 16MPa·m 1/2 .

实施例5： Example 5:

一种羟基磷灰石/钛酸钠复合生物陶瓷，包括以下质量份数的各个组分： A hydroxyapatite/sodium titanate composite bioceramic, comprising the following components in parts by mass:

羟基磷灰石42份、钛酸钠34份、纳米氧化钛8份、氧化锆5份、氮化硼4份、氧化铝7份和纳米氧化锌3份。 42 parts of hydroxyapatite, 34 parts of sodium titanate, 8 parts of nano-titanium oxide, 5 parts of zirconia, 4 parts of boron nitride, 7 parts of aluminum oxide and 3 parts of nano-zinc oxide.

根据本发明提供的制备方法制备羟基磷灰石/钛酸钠复合生物陶瓷，步骤如下： Prepare hydroxyapatite/sodium titanate composite bioceramics according to the preparation method provided by the present invention, the steps are as follows:

（1）称量：准确称取各个组分； (1) Weighing: Accurately weigh each component;

（2）球磨：将各个组分混合在一起，放入球磨机进行研磨混合； (2) Ball milling: Mix the components together and put them into a ball mill for grinding and mixing;

（3）冷压成型：将混合粉体采用60T压机进行压制； (3) Cold press forming: the mixed powder is pressed with a 60T press;

（4）将成型后的粉体放入模具中，进行高温煅烧，温度为1150℃，压力600MPa，时间5h； (4) Put the formed powder into the mold and perform high-temperature calcination at a temperature of 1150°C and a pressure of 600MPa for 5 hours;

（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/钛酸钠复合生物陶瓷。 (5) After calcination, take it out after cooling, and then obtain massive hydroxyapatite/sodium titanate composite bioceramics.

对得到的块状羟基磷灰石/钛酸钠复合生物陶瓷进行检测，检测生物陶瓷的性能：硬度820HV；压缩强度1080MPa；抗弯强度420MPa；韧性16MPa·m1/2。 The obtained massive hydroxyapatite/sodium titanate composite bioceramic was tested, and the properties of the bioceramic were tested: hardness 820HV; compressive strength 1080MPa; flexural strength 420MPa; toughness 16MPa·m 1/2 .

对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。 The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. a hydroxyapatite/Ti acid sodium composite boilogical ceramic, is characterized in that, be prepared from by each component of following mass fraction:
Hydroxyapatite 30-50 part, sodium titanate 20-40 part, nano-titanium oxide 5-10 part, zirconium white 3-7 part, boron nitride 2-6 part, aluminum oxide 5-10 part and nano zine oxide 2-5 part.
2. hydroxyapatite/Ti acid sodium composite boilogical ceramic according to claim 1, is characterized in that: the mass fraction of each component is: hydroxyapatite 35-45 part, sodium titanate 25-36 part, nano-titanium oxide 6-9 part, zirconium white 4-6 part, boron nitride 3-5 part, aluminum oxide 6-8 part and nano zine oxide 3-4 part.
3. hydroxyapatite/Ti acid sodium composite boilogical ceramic according to claim 2, is characterized in that: the mass fraction of each component is: hydroxyapatite 42 parts, sodium titanate 34 parts, nano-titanium oxide 8 parts, zirconium white 5 parts, boron nitride 4 parts, 7 parts, aluminum oxide and nano zine oxide 3 parts.
4. a preparation method for hydroxyapatite/Ti acid sodium composite boilogical ceramic according to claim 1, it is characterized in that, preparation process is as follows:
(1) weigh: accurately take each component;
(2) ball milling: each component mixed, puts into ball mill and carries out ground and mixed;
(3) coldmoulding: mixed powder is carried out coldmoulding;
(4) powder after shaping is put into mould, carry out high-temperature calcination, temperature is 1000 DEG C-1400 DEG C, pressure 300-800MPa, time 3-10h;
(5), after calcining, taking-up to be cooled, namely obtains block hydroxyapatite/Ti acid sodium composite boilogical ceramic.
5. the preparation method of hydroxyapatite/Ti acid sodium composite boilogical ceramic according to claim 4, is characterized in that: in step (4), the temperature of calcining is 1150 DEG C.
6. the preparation method of hydroxyapatite/Ti acid sodium composite boilogical ceramic according to claim 4, is characterized in that: in step (4), the pressure of calcining is 600MPa.
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