Glass-ceramic composite materials

Abstract

This invention provides a glass-ceramic composite material, which is a degradable and osteoconductive composite material composed of CaO-MgO-SiO2 (CMS glass) + CaMgSi2O6 (CMS ceramic) and CaSO4 (CS ceramic). In addition to CaO-MgO-SiO2 glass, this synthesized composite material mainly contains two ceramic phases: crystalline CaMgSi2O6 and CaSO4. CMS glass and CMS ceramic both have high mechanical strength, biocompatibility and osteoconductivity, while CaSO4 has the property of rapid degradation to promote bone inward growth.

Description

Technical Field

[0001] This invention relates to the field of glass-ceramic composite materials technology, and in particular to a composite material of CaO-MgO-SiO2 glass + CaMgSi2O6 ceramic (referred to as CMS glass-ceramic) and CaSO4 (CS ceramic). Background Technology

[0002] In modern medicine, the medical practice of inserting biomedical implants into the body to replace existing joints, intervertebral discs, or tooth roots is already a fairly mature technology. Therefore, research on the structure and materials of various biomedical implants has become one of the key development areas in the biomedical field.

[0003] Autologous materials (human bone) and allogeneic materials (animal bone) were first introduced as alternatives to bone grafts in the 1970s. However, synthetic materials (such as hydroxyapatite, tricalcium phosphate, calcium sulfate, and bioactive glass) have a commercial advantage due to their lower cost and mass production capabilities. Commercially available bioglasses are composed of silicon dioxide (SiO2), calcium oxide (CaO), sodium oxide (Na2O), and phosphorus pentoxide (P2O5), and are produced by simulating the dissociation of body fluids (SiO2). 4+ Ca 2+ Na + ,P 5+ The components stimulate new bone formation, and compared to other synthetic materials, it also has a greater ability to connect with bone and soft tissue. However, as a bone graft, bioactive glass is not degradable enough and needs to be combined with highly degradable bioceramic materials (calcium sulfate) to promote early osteoblast regeneration.

[0004] Among existing artificial bone materials, there are still problems that need to be overcome regarding whether they can provide the strength for human bone restoration and rehabilitation, whether they can be absorbed by the human body, and even whether they can promote the differentiation of human bone cells.

[0005] Therefore, after observing the above-mentioned issues, the inventor of this case came into being. Summary of the Invention

[0006] To achieve the above objectives, the present invention provides a degradable and osteoconductive glass-ceramic composite material for use in organisms and / or biomaterials. It mainly comprises a CaO-MgO-SiO2 glass phase, a CaMgSi2O6 crystalline phase, and a CaSO4 crystalline phase. The CaMgSi2O6 crystalline phase has high mechanical strength, biocompatibility, and osteoconductivity, while the CaSO4 crystalline phase has the property of rapid degradation to promote bone inward growth.

[0007] Preferably, the glass synthesis process of CaO-MgO-SiO2 includes the following steps: powder preparation, raw powder mixing, molten glass, and fine grinding of powder.

[0008] Preferably, in the powder preparation step, CaCO3:Mg(OH)2:SiO2 = 25:25:50 mol% + 8.5 wt% ZrO2 (glass-ceramic nucleating agent).

[0009] In the raw powder mixing step, powder:ball:water (20:60:20wt%) is mixed at 180rpm for 20 minutes, sieved using a suitable sieve, and dried in an oven at 170℃.

[0010] In the glass melting process, the temperature is set at 1500°C and held for 2 hours before the glass is water quenched.

[0011] In the fine grinding step, the powder is ground for an appropriate time using a grinder, mixed in the ratio of powder:ball:water = (13:79:8wt%), and ground to about 1μm. Then, it is sieved through a sieve and dried in an oven at 170℃ to complete the fabrication of CaO-MgO-SiO2 glass.

[0012] Next, the porous scaffold of the composite material of the present invention will be synthesized, and the proportions and steps are as follows: First, a slurry is prepared. CaO-MgO-SiO2 (CMS glass) and calcium sulfate dihydrate (CaSO4·2H2O, abbreviated as CS2H) are selected and powdered according to five different weight ratios of CMS:CS2H:3:0, 2:1, 1:1, 1:2, and 0:3. The powder is then mixed by rotor stirring (500 rpm, 5 min) at a powder:water:binder weight ratio of 50:31.2:18.8. Next, a sponge is soaked in the PU material and cut into 1.5 cm pieces using a hot-melt wire. 3 The sponge is then soaked in slurry and dried in a 170°C oven. Finally, the sponge is sintered at 800-1300°C for 2 hours, thus completing the synthesis of the porous scaffold of the CaO-MgO-SiO2 glass + CaMgSi2O6 ceramic and CaSO4 ceramic composite material of the present invention.

[0013] To enable those skilled in the art to understand the purpose, features and effects of the present invention, the present invention will be described in detail below with reference to the following specific embodiments and accompanying drawings.

[0014] [Simplified Explanation of the Diagram]

[0015] Figure 1 A graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention;

[0016] Figure 2A graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention;

[0017] Figure 3 A graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention;

[0018] Figure 4 A graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention;

[0019] Figure 5 A graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention;

[0020] Figure 6 This is a graph showing the experimental data of the properties of the glass-ceramic composite material according to the present invention.

Implementation Method

[0021] The glass-ceramic composite material of this invention is composed of CaO-MgO-SiO2 glass, CaMgSi2O6 ceramic, and CaSO4 ceramic. It is applied to organisms and / or biomaterials. Experiments have shown that the advantage of CS, a material traditionally used in artificial bone materials, is that it degrades rapidly to promote bone inward growth. In contrast, CMS in the glass-ceramic composite material of this invention has the advantages of high mechanical strength, high biocompatibility, and high osteoconductivity. This invention combines the two materials to form a glass-ceramic composite material.

[0022] The present invention relates to a degradable and osteoconductive glass-ceramic composite material, which mainly comprises CMS (CaO-MgO-SiO2 glass phase + CaMgSi2O6 crystalline phase) and CS (CaSO4 crystalline phase). Among them, the CaMgSi2O6 crystalline phase has high mechanical strength, biocompatibility and osteoconductivity, while the CaSO4 crystalline phase has the property of rapid degradation to promote bone inward growth.

[0023] Specifically, the glass synthesis process of CaO-MgO-SiO2 includes the following steps: powder preparation, raw powder mixing, molten glass, and fine grinding of powder.

[0024] Specifically, in the powder preparation step, CaCO3:Mg(OH)2:SiO2 (25:25:50 mol%) + 8.5 wt% ZrO2 (glass-ceramic nucleating agent).

[0025] In the raw powder mixing step, powder:ball:water (20:60:20wt%) is mixed at 180rpm for 20 minutes, sieved through a sieve, and dried in an oven at 170℃.

[0026] In the glass melting process, the temperature is set at 1500°C and held for 2 hours before the glass is water quenched.

[0027] In the powder fine grinding step, a grinder is used at 30g / 20min to mix powder:ball:water (13:79:8wt%) and grind to about 1μm. The mixture is then sieved and dried in an oven at 170℃ to complete the fabrication of CaO-MgO-SiO2 bioglass.

[0028] Next, the porous scaffold of the composite material of the present invention will be synthesized, and the proportions and steps are as follows: First, a slurry of CaO-MgO-SiO2 glass and CaSO4·2H2O ceramic will be prepared. Powders will be prepared according to five different weight ratios of CMS:CS2H:3:0, 2:1, 1:1, 1:2, and 0:3. The slurry will then be mixed with a powder:water:binder ratio of (50:31.25:18.75wt%) and stirred by a rotor (500rpm, 5min). Next, PU sponges will be soaked in the above-mentioned slurries of different proportions, and the sponges will be cut into 1.5cm pieces using a hot-melt wire. 3 The sponge was then soaked in slurry and dried in an oven at 170°C. Finally, the sponges soaked in different proportions of slurry (CMS:CS2H weight ratio = 3:0, 2:1, 1:1, 1:2wt) were sintered at 900°C for 2 hours, while the sponges soaked in slurry (CMS:CS2H weight ratio = 0:3wt) were sintered at 1100°C for 1 hour, thus completing the synthesis of the porous scaffold of the composite material of the present invention.

[0029] Specifically, the experimental properties and data of the composite material of the present invention are as follows: Figures 1-6 As shown.

[0030] In the porosity portion of the composite material, from Figure 1 As can be seen, when the weight ratio of CMS to CS2H is 3:0, 2:1, 1:1, 1:2 and 0:3, the porosity of the composite materials with the other ratios, except for the composite material containing only CMS, is greater than 70%, which meets the standard.

[0031] In the mechanical strength section of composite materials, from Figure 2 As can be seen, when the weight ratio of CMS:CS2H is 3:0 and 2:1, it has better mechanical strength.

[0032] Regarding the pH value of the degraded composite material, generally speaking, a pH value between 7 and 8 is most suitable for cell growth. Therefore, through... Figure 3 As can be seen, after soaking in Tris-HCl solution for 120 hours, the pH value of the composite material of the present invention after degradation is between 7 and 8 when the weight ratio of CMS:CS2H is 3:0, 2:1, 1:1, 1:2 and 0:3.

[0033] In the measurement of weight loss after composite material degradation, greater weight loss indicates more ion release, which is beneficial to bone cell growth, resulting in a better effect. Figure 4 As can be seen, when the weight ratio of CMS to CS2H is 3:0, 2:1, 1:1, 1:2 and 0:3, the composite material of the present invention under the condition containing CS2H has a significant weight loss, that is, it has a faster degradation rate, which can promote the growth of early osteocytes into the bone.

[0034] In the experimental section on the ion concentration released by the degradation of composite materials, from Figure 5 and Figure 6 As can be seen, when the weight ratio of CMS:CS2H is 3:0, 2:1, 1:1, 1:2 and 0:3, the composite material will develop into (CaO-MgO-SiO2+CaMgSi2O6). x (CaSO4) y CMS (short for CMS) x CS y CMS x CS y After degradation, Ca, Mg, Si, and S ions are obtained. Figure 5 It was found that CMS glass-ceramics exhibit low degradation performance in citric acid solutions, while CMS glass-ceramics composites containing CS calcium sulfate show higher degradation performance. Figure 6 It was found that in Tris-HCl simulated body fluid, the concentration of ions released from the degradation of CMS glass ceramics was higher than that of composite materials containing CS calcium sulfate.

[0035] Specifically, the preferred weight ratio of CMS to CS in glass-ceramic composites is between 3:0 and 1:2.

[0036] Finally, the technical features of this invention and the technical effects it can achieve are summarized as follows:

[0037] Firstly, the glass-ceramic composite material of the present invention improves biocompatibility.

[0038] Secondly, the glass-ceramic composite material according to the present invention rapidly degrades to promote inward bone growth.

[0039] Thirdly, the glass-ceramic composite material according to the present invention has high mechanical strength and high osteoconductivity.

[0040] The above describes the implementation of the present invention through specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0041] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention; any equivalent changes or modifications made without departing from the spirit disclosed in the present invention should be included within the scope of the patent.

Claims

1. A glass-ceramic composite material, characterized in that, The glass-ceramic composite material contains: The glass-ceramic composite material is made of CaO-MgO-SiO2, CaMgSi2O6 and CaSO4, wherein CaO-MgO-SiO2 is the glass phase, CaMgSi2O6 is the crystalline phase, and CaSO4 is the crystalline phase. The glass-ceramic composite material is made by sintering CaO-MgO-SiO2 glass and CaSO4·2H2O in a weight ratio of 2:1, 1:1 or 1:2.

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