CN101456751B - A method for preparing calcium phosphate-based bioceramics by adding zinc oxide whiskers - Google Patents

Abstract

The invention relates to a method for preparing calcium phosphate-based bioceramics by adding zinc oxide whiskers, and belongs to the scientific field of inorganic non-metallic materials. The basic implementation steps of the present invention are as follows: take TCP/HAP nanocomposite powder as the main raw material, add different amounts of ZnOw respectively, and mix uniformly by mechanical mixing; carry out cold pressing molding under a molding pressure of 40MPa, and form the sample after molding Sintered in a high-temperature furnace, the obtained sample has good mechanical properties and good biocompatibility, and the biodegradation rate matches the growth rate of the bone; the advantages of the present invention are simple equipment, low investment, low production cost, and high performance of the obtained product. High, controllable product performance and other advantages.

Description

A method for preparing calcium phosphate-based bioceramics by adding zinc oxide whiskers

technical field

The invention relates to a method for preparing calcium phosphate-based bioceramics by adding zinc oxide whiskers, which belongs to the scientific field of inorganic non-metallic materials and can be used in the fields of preparation of bone graft materials and the like.

Background technique

Calcium phosphate-based bioceramics have been widely used in medicine because of their similar composition to natural bone and good biocompatibility. Calcium phosphate bioceramics mainly include tricalcium phosphate and hydroxyapatite.

The biggest advantage of tricalcium phosphate (TCP) is its good biocompatibility, and it can directly fuse with the bone after implantation without any rejection and adverse reactions. Studies have shown that calcium phosphate ceramics not only have the effect of bone conduction, but also have the effect of inducing osteogenesis. However, its degradation rate is too fast, and it is completely degraded before the new bone grows in. Can not achieve the purpose of bone replacement.

Hydroxyapatite (HAP) is the main inorganic component of hard tissue in the human body. In the early 1970s, Hideki Aoki of Japan and Jarcho of the United States synthesized HAP for the first time. It is one of the hot topics in the field of biomedical materials research. HAP has good biocompatibility and osteoconductivity, can be well combined with human bone, and has a certain induction effect on new bone growth. However, pure HAP has unsatisfactory physical and mechanical properties, high brittleness, poor degradation performance, and is not easy to degrade in vivo, which slows down the growth of new bone.

In summary, neither tricalcium phosphate nor hydroxyapatite alone can complete bone replacement surgery, so it is necessary to develop a new type of composite material; adding various materials to prepare calcium phosphate-based bioceramics has become a research field in this field. One of the hot spots.

Zinc has a special direct stimulating effect on the proliferation of osteoblasts, but has a certain inhibitory effect on osteoclasts. Animal experiments and clinical experiments also show that zinc can stimulate bone growth, which is beneficial to improve the bioactivity and degradation performance of biomaterials; in addition, the addition of zinc oxide whiskers (ZnOw) can also improve the mechanical strength of calcium phosphate-based materials. Therefore, ZnOw-doped calcium phosphate-based ceramics are expected to become a new generation of bone tissue engineering materials. Moreover, the technology of preparing calcium phosphate-based bioceramics by doping ZnOw has not been reported so far.

Contents of the invention

The purpose of the invention is to prepare calcium phosphate-based bioceramic with excellent performance by using the method of adding zinc oxide whiskers.

Technical scheme of the present invention is:

1) Ingredients: use tricalcium phosphate and hydroxyapatite nanocomposite powder as main raw materials, wherein the ratio of tricalcium phosphate to hydroxyapatite is 1:2-5:2;

2) adding zinc oxide whiskers to the composite powder in step 1) as a sintering aid and a toughening agent, the amount added is 1wt%-3wt%;

3) Add a certain amount of binder to the powder obtained in step 2), the binder is the alcohol solution of PVB; the ratio of composite powder mass to binder volume is 1: 1-1: 2 (g/ mL), using the method of mechanical mixing to uniformly mix it for 1-3 hours, and the mixing medium is absolute ethanol;

4) Sieve the uniformly mixed raw materials, the particle size is 60-200 mesh, and then cold press molding according to needs;

5) Sinter the sample obtained by cold pressing in a high-temperature furnace at a temperature of 1000-1300°C, keep it warm for 120-300 minutes after reaching the set temperature, and cool naturally to room temperature with the furnace to obtain the product.

Beneficial effect

The technology that the present invention proposes by adding ZnOw to prepare calcium phosphate-based bioceramics has the following prominent advantages:

1) The equipment is simple; less investment;

2) Low production cost;

3) The obtained sample has good mechanical properties and good biocompatibility, and the biodegradation rate matches the growth rate of bone;

4) The performance of the product is controllable, and products with different properties can be obtained by adjusting the ratio of TCP to HAP and the amount of added zinc oxide whiskers.

Description of drawings

Fig. 1 contains the XRD figure of 1% ZnOw sample after sintering;

Fig. 2 contains the XRD pattern after sintering of 1.5% ZnOw sample;

Fig. 3 contains the XRD figure of 2% ZnOw sample after sintering;

Fig. 4 contains the XRD figure of 2.5% ZnOw sample after sintering;

Fig. 5 contains the XRD figure of 3% ZnOw sample after sintering;

Fig. 6 contains the SEM image of 1% ZnOw sample after sintering;

Fig. 7 contains the SEM image of 1.5% ZnOw sample after sintering;

Fig. 8 contains the SEM image of 2% ZnOw sample after sintering;

Fig. 9 contains the SEM image of 2.5% ZnOw sample after sintering;

Fig. 10 contains the SEM image of 3% ZnOw sample after sintering;

Figure 11 is the SEM image of the sample degraded in simulated body fluid for 15 days;

Detailed ways

The present invention will be further described below in conjunction with drawings and embodiments.

Example 1

The nanocomposite powder that is 3: 2 is main raw material with TCP and HAP ratio, adds 1wt% zinc oxide whisker, and adds the PVB alcohol solution that content is 3wt%, the ratio of composite powder quality and PVB alcohol solution volume is: 1:1.5 (g/mL); fully mixed with absolute ethanol as the mixed medium, passed through a 60-mesh sieve after drying; cold-pressed at a molding pressure of 40MPa, and the molded sample was placed in a high-temperature furnace Sintering, the sintering temperature is 1200°C, and the holding time is 180min; the obtained sample is analyzed by XRD and SEM; the results are shown in Figure 1 and Figure 6.

Example 2

The nanocomposite powder that is 3: 2 is main raw material with TCP and HAP ratio, adds 1.5wt% ZnOw, and adds the PVB alcohol solution that content is 3wt%, the ratio of composite powder quality and PVB alcohol solution volume is: 1: 1.5 (g/mL); fully mixed with absolute ethanol as the mixed medium, passed through a 60-mesh sieve after drying; cold-pressed at a molding pressure of 40MPa, and the molded sample was sintered in a high-temperature furnace. The sintering temperature was 1200°C, and the holding time was 180 minutes; the obtained samples were analyzed by XRD and SEM; the results are shown in Figure 2 and Figure 7 .

Example 3

The nano-composite powder with a ratio of TCP and HAP of 3:2 is the main raw material, 2wt% ZnOw is added, and a PVB alcohol solution with a content of 3wt% is added. The ratio of the composite powder mass to the volume of the PVB alcohol solution is: 1:1.5 (g/mL); fully mixed under the condition of anhydrous ethanol as the mixed medium, passed through a 60-mesh sieve after drying; cold-pressed molding was carried out under a molding pressure of 40MPa, and the molded sample was placed in a high-temperature furnace for sintering, and then sintered The temperature was 1200°C, and the holding time was 180 minutes; XRD and SEM analysis were performed on the obtained sample; the results are shown in Figure 3 and Figure 8 .

Example 4

The nanocomposite powder that is 3: 2 is main raw material with TCP and HAP ratio, adds 2.5wt% ZnOw, and adds the PVB alcohol solution that content is 3wt%, the ratio of composite powder quality and PVB alcohol solution volume is: 1: 1.5 (g/mL); fully mixed with absolute ethanol as the mixed medium, passed through a 60-mesh sieve after drying; cold-pressed at a molding pressure of 40MPa, and the molded sample was sintered in a high-temperature furnace. The sintering temperature was 1200°C, and the holding time was 180 minutes; the obtained samples were analyzed by XRD and SEM; the results are shown in Figure 4 and Figure 9 .

Example 5

The nano-composite powder with a ratio of TCP and HAP of 3:2 is the main raw material, 3wt% ZnOw is added, and a PVB alcohol solution with a content of 3wt% is added. The ratio of the composite powder mass to the volume of the PVB alcohol solution is: 1:1.5 (g/mL); fully mixed under the condition of anhydrous ethanol as the mixed medium, passed through a 60-mesh sieve after drying; cold-pressed molding was carried out under a molding pressure of 40MPa, and the molded sample was placed in a high-temperature furnace for sintering, and then sintered The temperature was 1200°C, and the holding time was 180 minutes; XRD and SEM analysis were performed on the obtained sample; the results are shown in Figure 5 and Figure 10 .

The flexural strength of the sample obtained in the above examples is not less than 40MPa, and its degradation performance is tested in a simulated body fluid at 37°C, and its degradation rate is basically consistent with the bone ingrowth rate (Figure 11).

Claims (1)

1. a method for preparing calcium phosphate-based bioceramics by adding zinc oxide whiskers, is characterized in that the preparation steps are: 1) Ingredients: use tricalcium phosphate and hydroxyapatite nanocomposite powder as main raw materials, wherein the ratio of tricalcium phosphate and hydroxyapatite is 1:2-5:2; 2) adding zinc oxide whiskers to the composite powder in step 1) as a sintering aid and a toughening agent, the amount added is 1wt%-3wt%; 3) Add a certain amount of binder to the powder obtained in step 2), the binder is an alcohol solution of PVB; the ratio of the composite powder mass to the volume of the binder is 1:1-1:2, compound The unit of the ratio of powder mass to binder volume is g/mL, and it is uniformly mixed for 1-3 hours by mechanical mixing method, and the mixing medium is absolute ethanol; 4) Sieve the uniformly mixed raw materials, the particle size is 60-200 mesh, and then cold press molding according to needs; 5) Sinter the sample obtained by cold pressing in a high-temperature furnace at a temperature of 1000-1300°C, keep it warm for 120-300 minutes after reaching the set temperature, and cool naturally to room temperature with the furnace to obtain the product.

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