CN100406069C - A kind of CaO-P2O5-Na2O-TiO2-ZrO2 biological glass ceramics and its preparation method - Google Patents

Abstract

The invention relates to a CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramic and a preparation method thereof. In the glass ceramic, the total content of CaO and P ₂ O ₅ is 80-90 mol%, and the Na ₂ O The content of TiO ₂ and ZrO ₂ is 4~7mol%. The preparation process is as follows: mix the raw materials evenly, heat and melt them after drying, then take them out and pour them on the stainless steel plate to punch them to make glass; grind the punched glass balls into powder, cold press them into blocks and sinter them to obtain glass ceramics. The glass-ceramic does not contain SiO ₂ , has no toxic elements, and has good biological activity. After soaking in simulated human body fluid for 4 days, a layer of dense and uniform hydroxyapatite is formed; it has high strength (greater than 90MPa), and can be cut. Easy to process; with high Ca/P ratio and composition similar to human hard tissue, it can be used as a replacement and repair material for human hard tissue. The bioglass-ceramic has the generality of bioglass-ceramics, and it is expected to obtain faster bone formation and higher bone bonding strength compared with metal implants.

Description

A kind of CaO-P2O5-Na2O-TiO2-ZrO2 biological glass ceramics and its preparation method

Technical field:

The invention relates to the field of glass ceramics, in particular to CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics with high strength and high biological activity for clinical medicine application and a preparation method thereof.

Background technique:

生物玻璃(Na₂O-CaO-SiO₂-P₂O₅系)、Ceravital微晶玻璃(Na₂O-K₂O-MgO-CaO-P₂O5-SiO₂系)、A-W生物玻璃陶瓷(MgO-CaO-SiO₂-P₂O₅系)、羟基磷灰石生物活性陶瓷(HA，组成为：Ca₁₀(PO₄)₆(OH)₂)等等，见参考文献[2]和[3]，参考文献[2]：Larry L.Hench.Bioceramics.J.Am.Ceram.Soc.1998，81[7]：1705-1728；参考文献[3]：杨为中，周大利，尹光福和郑昌琼.生物医学工程学杂志.2003，20(3)：541-545。和其它生物惰性材料相比，生物玻璃陶瓷具有更好的生物相容性、更高的骨键合强度和更快的成骨能力，见参考文献[4]：李玉宝.生物医学材料.北京：化学工业出版社，2003：82。但是大多数生物活性玻璃都含有大量的SiO₂，而Nagase et al.发现在实验老鼠腹腔注射含二氧化硅钙磷玻璃的当量盐水时老鼠死亡，而不含二氧化硅时则不显示毒性，见参考文献[5]：Nagase M，Abe Y，Chigira M and Udagawa E.Toxicity of silica-containing calciumposphate glasses demonstrated in mice.Biomaterials.1992，13：172-175。Human hard tissue repair and reconstruction materials are the earliest and most mature field of biomedical materials. So far, materials used for hard tissue repair and replacement include metals and alloys, bioglass ceramics, polymers, composite materials, and bone derivatives of humans and animals, etc., see reference [1]: Yu Yaoting. Biomedical Materials. Tianjin : Tianjin University Press, 2000: 116. Bioactive glass ceramics are a class of biomaterials that can bond with biological soft tissue or bone tissue, and have incomparable advantages over metals, polymers, and bioinert materials. As a result, there has been strong interest in this class of novel materials, and a variety of bioactive glass-ceramics have been developed, such as:

Bioglass (Na ₂ O-CaO-SiO ₂ -P ₂ O ₅ series), Ceravital glass ceramics (Na ₂ OK ₂ O-MgO-CaO-P ₂ O5-SiO ₂ series), AW bioglass ceramics (MgO- CaO-SiO ₂ -P ₂ O ₅ series), hydroxyapatite bioactive ceramics (HA, composed of: Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), etc., see references [2] and [3] , Reference [2]: Larry L.Hench.Bioceramics.J.Am.Ceram.Soc.1998, 81[7]: 1705-1728; Reference [3]: Yang Weizhong, Zhou Dali, Yin Guangfu and Zheng Changqiong. Biomedicine Journal of Engineering. 2003, 20(3): 541-545. Compared with other biologically inert materials, bioglass ceramics have better biocompatibility, higher bone bonding strength and faster bone formation ability, see reference [4]: Li Yubao. Biomedical Materials. Beijing: Chemical Industry Press, 2003: 82. However, most bioactive glasses contain a large amount of SiO ₂ , and Nagase et al. found that mice died when intraperitoneally injected with the equivalent saline containing silicon dioxide calcium phosphorus glass, but did not show toxicity when there was no silicon dioxide, See reference [5]: Nagase M, Abe Y, Chigira M and Udagawa E. Toxicity of silica-containing calcium phosphate glasses demonstrated in mice. Biomaterials. 1992, 13: 172-175.

Bioglass-ceramic is clinically used as a bone substitute material through osteoconduction. Due to its good biocompatibility, it does not cause obvious reactions after being implanted in the body. The host callus around the implant can converge through the crawling surface and wrap the implant so that it can fill and connect the bone defect. But its low toughness limits its popularization and application. Zirconia ceramics are a newly developed very important structural ceramics second only to alumina. Because of its good properties, such as high hardness, high strength and high fracture toughness, it has attracted more and more attention. See reference [6]: Liu Weiliang. Advanced Ceramic Technology. Wuhan: Wuhan University of Technology Press. 2004: 176-180. Zirconia has long been added to glass ceramics as a crystal nucleating agent. Adding zirconia particles to the glass composition can increase the breaking strength of the glass from 2MPa to 3MPa, see reference [7]: Tang Jiwen, Zhang Yude and Liu Chunmei. Research progress of bioactive glass ceramic artificial bone materials. Shandong Medicine. 1997, 37 [5]: 45-50. CaO-P ₂ O ₅ series glass ceramics is a new type of biological glass ceramics recently developed. The composition of this series of ceramics is close to that of human bone tissue. It has good biological activity and is non-toxic. See reference [8]: Kasuga T and Abe Y. Calcium phosphate invert glasses with soda and titania. J. Non-cryst. Solids. 1999, 243:70-74. The present invention introduces ZrO ₂ on the basis of CaO-P ₂ O ₅ series glass ceramics to form CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ series glass ceramics. It is a kind of bioglass without SiO ₂ , has a high Ca/P ratio and a composition similar to that of human hard tissue, has high breaking strength and biological activity, and is more suitable as a human implant material.

Contents of the invention

The object of the present invention is to provide a novel CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramic and its preparation method. The glass-ceramic has good biological activity, relatively high hardness, strength and machinability, has a composition similar to that of human hard tissue, and can be used as a replacement and repair material for human hard tissue.

Technical scheme of the present invention is:

The invention provides a CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramic, the total content of CaO and P ₂ O ₅ is 80-90 mol%, the content of Na ₂ O is 4-7 mol%, The rest are TiO ₂ and ZrO ₂ .

In the CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the invention, in the glass ceramics, the molar ratio of Ca to P is 0.5-1.5.

In the CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the invention, the content of ZrO ₂ in the glass ceramics is 0.5-10 mol%.

The preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the present invention includes the preparation of glass and the preparation of ceramics, and the specific steps are as follows:

(1) Preparation of glass

Using CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ as raw materials, mix the raw materials evenly according to the stated ingredients, prepare glass slurry, grind it after drying, heat and melt it, then take it out and pour it on the stainless steel plate stamping;

(2) Preparation of ceramics

The punched glass balls are ground into powder, cold pressed into blocks and sintered.

In the step 1, the glass slurry is dried and crushed, and the particle size of the crushed powder is 5-10 μm.

In the step 1, heat and melt at 1300-1400° C., hold the temperature for 0.5-1 hour, take out immediately and pour it on the stainless steel plate to punch the glass.

In the step 2, the glass ball obtained by punching is ground into powder, and the particle size of the powder is 1-10 μm.

In the step 2, the cold pressing pressure is 80-150 MPa, the glass powder sintering temperature is 800-850° C., and the time is 1-2/hour.

In the preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the present invention, the raw materials used in the glass are chemical reagents: CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ (liquid, 85% by weight), all of which are analytically pure.

In the preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the present invention, uniform and dense hydroxyapatite is formed on the surface after soaking in simulated human body fluid for 4-7 days, and the surface activity high.

生物玻璃。According to the preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics provided by the present invention, the bending strength of the prepared ceramics is greater than 90MPa, which is better than

bioglass.

The CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ series glass ceramics provided by the invention have good biological activity, and hydroxyapatite is formed on the surface after soaking in simulated human body fluid (SBF) for 4-7 days. Its good biological activity and mechanical properties can not only be used as teeth, maxillofacial bone and middle ear bone, but also as medical materials such as artificial vertebral body, intervertebral disc and iliac crest.

The beneficial effects of the present invention are:

The glass-ceramic of the present invention does not contain SiO ₂ , has no toxic elements, and has good biological activity. After soaking in simulated human body fluid for 4 days, a layer of dense and uniform hydroxyapatite is formed; it has high strength (greater than 90MPa), and can be cut , easy to process; with a high Ca/P ratio and similar composition to human hard tissue, it can be used as a replacement and repair material for human hard tissue. The bioglass-ceramic has the generality of bioglass-ceramics, and it is expected to obtain faster bone formation and higher bone bonding strength compared with metal implants.

Description of drawings:

Figure 1 CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass obtained by rapid stamping;

Fig. 2 The morphology of 60CaO30P ₂ O ₅ 4Na ₂ O3TiO ₂ 3ZrO ₂ glass obtained by rapid stamping after grinding with 1000# sandpaper;

Figure 360 Topography of CaO30P ₂ O ₅ 4Na ₂ O3TiO ₂ 3ZrO ₂ glass soaked in simulated human body fluid for 4 days;

Figure ₄₆₀ The enlarged photo of _the topography of _{CaO30P2O54Na2O3TiO23ZrO2 glass} soaked in simulated _human body fluid for 4 days;

Figure 560 Topography of CaO30P ₂ O ₅ 5Na ₂ O3TiO ₂ 2ZrO ₂ glass soaked in simulated human body fluid for 7 days;

_{Fig .} 660 CaO30P2O55Na2O3TiO22ZrO2The _X -ray diffraction spectrum of _glass simulated human body fluid _soaked in 7 days;

Fig. 7 Glass ceramics obtained after CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass pulverization, cold pressing and sintering;

Figure 860CaO30P ₂ O ₅ 5Na ₂ O3TiO ₂ 2ZrO ₂ The composition diffraction pattern of glass ceramics;

Fig. 960 Topography of CaO30P ₂ O ₅ 4Na ₂ O3TiO ₂ 3ZrO ₂ glass-ceramics soaked in simulated human body fluid for 7 days.

Detailed ways:

Example 1

Use analytically pure CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ (85%) as raw materials to prepare a glass slurry with the ingredients described in Table 1, mix the raw materials evenly with an electric mixer, and then place at 50°C Dry in a drying oven for 24 hours. Pound the dried raw material into powder (with a particle size of 5-10 μm) and place it in a platinum crucible at 1350°C for 0.5h, take it out immediately, pour it on a stainless steel plate, and press it quickly to obtain glass. The macroscopic morphology of the obtained glass is shown in Fig. 1 .

Table 1CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass components

Example 2

After soaking the punched 60CaO30P ₂ O ₅ 4Na ₂ O3TiO ₂ 3ZrO ₂ glass in simulated human body fluid (Table 2) at 37°C for 4 days, a layer of dense and uniform hydroxyapatite formed on the surface. The microscopic morphology before soaking is shown in Figure 2, and the microscopic morphology after soaking is shown in Figure 3 and Figure 4.

Table 2 Ion concentrations (mM) in plasma and simulated body fluid (SBF) in the human body

Example 3

After soaking the punched 60CaO30P ₂ O ₅ 5Na ₂ O3TiO ₂ 2ZrO ₂ glass in simulated human body fluid (Table 2) at 37°C for 7 days, a layer of dense and uniform hydroxyapatite was formed on the surface. The microscopic morphology after soaking is shown in Figure 5, and its X-ray diffraction pattern is shown in Figure 6.

Example 4

The stamped glass was pulverized by a ball mill and then cold-pressed into a 40×9×6mm sample with a cold-pressing pressure of 100 MPa. The temperature was raised with the furnace at a rate of 10°C/min, kept at 850°C for 1 hour, and cooled with the furnace. The macroscopic morphology of the obtained ceramics is shown in Fig. 7, and its main components are β-Ca ₃ (PO ₄ ) ₂ and β-Ca ₂ P ₂ O ₇ (as shown in Fig. 8 ).

Example 5

After soaking the punched 60CaO30P ₂ O ₅ 5Na ₂ O3TiO ₂ 2ZrO ₂ glass ceramics in simulated human body fluid (Table 2) at 37°C for 7 days, a layer of dense and uniform hydroxyapatite was formed on the surface. The microscopic morphology after soaking is shown in Fig. 9.

Example 6

生物玻璃。A three-point bending test was carried out on the ceramics obtained by crushing the punched glass through a ball mill, cold pressing and sintering. The test results showed that the bending strength of the CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ series glass ceramics was greater than 90 MPa, which outperform

bioglass.

Example 7

Use analytically pure CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ (liquid, 85% by weight) as raw materials to prepare a glass slurry with the ingredients described in Table 1, and mix the raw materials evenly with an electric mixer. Then place it in a drying oven at 50°C for 24 hours. Pound the dried raw material into powder (with a particle size of 5-10 μm) and place it in a platinum crucible at 1300°C for 1 hour, take it out immediately, pour it on a stainless steel plate, and press it quickly to obtain glass.

Table 3 CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass components

After soaking the stamped glass in simulated human body fluid (Table 2) at 37°C for 7 days, a layer of dense and uniform hydroxyapatite was formed on the surface with high surface activity.

The stamped glass was pulverized by a ball mill and then cold-pressed into a 40×9×6mm sample with a pressure of 150 MPa, then heated up with the furnace at a rate of 10°C/min, kept at 800°C for 2 hours, and cooled with the furnace. The macroscopic morphology of the obtained ceramics is mainly composed of β-Ca ₃ (PO ₄ ) ₂ and β-Ca ₂ P ₂ O ₇ .

After soaking the punched glass-ceramics in simulated human body fluid (Table 2) at 37°C for 7 days, a dense and uniform layer of hydroxyapatite was formed on the surface. Ear bones can also be used as medical materials such as artificial vertebral bodies, intervertebral discs and iliac crests.

Example 8

Use analytically pure CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ (liquid, 85% by weight) as raw materials to prepare a glass slurry with the ingredients described in Table 1, and mix the raw materials evenly with an electric mixer. Then place it in a drying oven at 50°C for 24 hours. Pound the dried raw material into powder (with a particle size of 5-10 μm) and place it in a platinum crucible at 1400°C for 0.8 hours, take it out immediately, pour it on a stainless steel plate, and press it quickly to obtain glass.

Table 4 CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ glass components

After soaking the stamped glass in simulated human body fluid (Table 2) at 37°C for 7 days, a layer of dense and uniform hydroxyapatite was formed on the surface with high surface activity.

The stamped glass was pulverized by a ball mill and then cold-pressed into a 40×9×6mm sample with a pressure of 80 MPa, then heated up with the furnace at a rate of 10°C/min, kept at 800°C for 2 hours, and cooled with the furnace. The macroscopic morphology of the obtained ceramics is mainly composed of β-Ca ₃ (PO ₄ ) ₂ and β-Ca ₂ P ₂ O ₇ .

After soaking the punched glass-ceramics in simulated human body fluid (Table 2) at 37°C for 7 days, a dense and uniform layer of hydroxyapatite was formed on the surface. Ear bones can also be used as medical materials such as artificial vertebral bodies, intervertebral discs and iliac crests.

Claims (8)

1. A CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics, characterized in that: the total content of CaO and P ₂ O ₅ is 80-90 mol%, and the content of Na ₂ O is 4-90 mol%. 7mol%, and the rest are TiO ₂ and ZrO ₂ . 2. The CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass-ceramic according to claim 1, characterized in that: in the glass-ceramic, the molar ratio of Ca to P is 0.5-1.5. 3. The CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass-ceramic according to claim 1, characterized in that the content of ZrO ₂ in the glass-ceramic is 0.5-10 mol%. 4. According to the preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics according to claim 1, it is characterized in that it includes the preparation of glass and the preparation of ceramics, and the specific steps are as follows: (1) Preparation of glass Using CaCO ₃ , Na ₂ CO ₃ , TiO ₂ , ZrO ₂ and H ₃ PO ₄ as raw materials, mix the raw materials evenly according to the ingredients described in claim 1, and prepare glass slurry, which is dried, crushed, heated and melted, and then taken out and poured on Stamping on stainless steel plate; (2) Preparation of ceramics The punched glass balls are ground into powder, cold pressed into blocks and sintered. 5. According to the preparation method of CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass ceramics according to claim 4, it is characterized in that: in the step 1, the glass slurry is dried and crushed, The particle size of the crushed powder is 5-10 μm. 6. The method for preparing CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass-ceramics according to claim 4, characterized in that: in step 1, heating and melting at 1300-1400°C 1. After holding time for 0.5 to 1 hour, immediately take out the glass and pour it on the stainless steel plate to punch the glass. 7. The method for preparing CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass-ceramics according to claim 4, characterized in that: in the step 2, the glass balls obtained by punching are ground into powder , The particle size of the powder is 1-10 μm. 8. The method for preparing CaO-P ₂ O ₅ -Na ₂ O-TiO ₂ -ZrO ₂ biological glass-ceramics according to claim 4, characterized in that: in the step 2, the cold pressing pressure is 80-150 MPa, The sintering temperature of the glass powder is 800-850° C., and the time is 1-2 hours.

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