CN110152057B - Preparation method of reinforced bioglass bone repair material - Google Patents

Preparation method of reinforced bioglass bone repair material Download PDF

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CN110152057B
CN110152057B CN201910285095.9A CN201910285095A CN110152057B CN 110152057 B CN110152057 B CN 110152057B CN 201910285095 A CN201910285095 A CN 201910285095A CN 110152057 B CN110152057 B CN 110152057B
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polyoxyethylene
bioglass
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polyoxypropylene
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廖先传
廖书辉
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Hubei Shuangxing Pharmaceutical Co ltd
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention provides a preparation method of a reinforced bioglass bone repair material, wherein bioglass bone is Na2O‑CaO‑SiO2‑P2O5The system is prepared by taking a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer as a template and monoclinic Ca with the length-diameter ratio of 10: 1-20: 11‑δMgδSi2O2N2(delta is more than or equal to 0.01 and less than or equal to 0.1) is taken as a reinforcing phase. The invention forms three-dimensional through large pore channels with better distribution by a soft template method of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, decomposes sodium citrate and calcium carbonate to form small pores, decomposes carbon fiber to form middle pores, has three pores with different sizes to match, and simultaneously has (Ca, Mg) Si2O2N2The reinforcing phase has a short rod-shaped structure, can be mutually crossed in a bioglass system, and can keep the integral characteristics of bioglass and obviously improve the mechanical strength under the synergistic action of other components.

Description

Preparation method of reinforced bioglass bone repair material
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of biomedical materials, and particularly relates to a preparation method of a reinforced bioglass bone repair material.
[ background of the invention ]
Biomedical materials are novel high-tech materials that interact with biological systems to repair, treat, synthesize, or replace damaged tissues and organs, and minimize adverse effects on human tissues and blood. According to the properties of the materials, the biomedical materials comprise high molecular materials, metal materials, inorganic non-metal materials, natural biological materials and the like. Bioglass is an important branch of biomedical materials, mainly composed of silicate glass materials, and the main component is SiO2And CaO, a class of inorganic non-metallic materials. Because the bioglass has good biocompatibility, no toxicity and high bioactivity, the bioglass can be used for repairing, regenerating and replacing organs such as bones, teeth and the like. The bioglass has the capacity of inducing the proliferation and the differentiation of osteocytes and promoting the growth of the osteocytes, and can strongly connect hard tissues and soft tissues of a human body. The bioglass has specific chemical composition, and inorganic ions (such as silicon, phosphorus, calcium, sodium, etc.) dissolved out from the bioglass can promote the expression of genes and the differentiation of cells to osteoblasts, promote the proliferation and differentiation of osteoblasts and further form firm bone tissue with the bone tissueHas good bone repairing performance.
Medical research shows that the bioactive glass used for bone filling and repairing needs to have a three-dimensional porous and intercommunicated pore structure with proper size so as to facilitate infiltration of tissue fluid and growth of bone cells into the material, promote bone tissue repair and improve the success rate of surgery. Therefore, to be successful as a bone graft implant, the bioactive glass must be both porous and form a certain pore size distribution. At present, pore-forming agents are commonly used for pore-forming on bioactive glass materials, and materials such as ammonium bicarbonate, urea, carbon powder, benzoic acid, polyvinyl alcohol, hydroxymethyl cellulose and the like are commonly used, but the ideal effects are not achieved, and further development is still needed, for example, CN105621892 discloses a pore-forming agent which is formed by mixing urea, polyethylene glycol and starch and is used for improving porosity and uniformly distributing. On the other hand, although some pore-forming agents can form three-dimensional through-channels at present, the mechanical strength of the bioglass is low, the brittleness is high, the bending strength is low, and the mechanical property is further reduced due to the necessary porous structure, so that the effect of repairing a larger range of bone defects is influenced to a certain extent. In the prior art, the compressive strength of the bioglass porous material (porosity is more than 70 percent) is generally between 0.2 and 2.0MPa, and the bioglass porous material can only be used for repairing bone repair materials with ideal body positions and low bearing capacity, such as ear bones, finger bones and the like, so that the mechanical strength is improved while the through hole is maintained, and the bioglass porous material is an important development direction of bioglass bone repair materials.
[ summary of the invention ]
The invention provides a preparation method of a reinforced bioglass bone repair material, which is characterized in that three-dimensional through holes with better distribution are formed by a soft template method, and (Ca, Mg) Si is added2O2N2The reinforcing phase can provide pores necessary for bone growth and ensure a proper degradation rate while improving mechanical strength.
The technical solution of the invention is as follows:
the preparation method of the reinforced bioglass bone repair material is characterized in that bioglass bone is Na2O-CaO-SiO2-P2O5The system is prepared by taking a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer as a template and Ca with the length-diameter ratio of 10: 1-20: 11-δMgδSi2O2N2(delta is more than or equal to 0.01 and less than or equal to 0.1) is taken as a reinforcing phase. The polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymer is an amphiphilic molecule, forms multi-molecule aggregated micelles in aqueous solution spontaneously, has good dispersibility, can realize self-assembly with hydrogen bonds existing in large amount in tetraethyl orthosilicate (TEOS) in mixed slurry, and can generate three-dimensional network-shaped large pore canals after a template agent is removed at high temperature. CaSi2O2N2Is a nitrogen-containing crystalline phase with a small amount of Mg2+Substituted Ca2+The glass bone can generate rod-shaped crystal grains, can effectively improve the mechanical strength of the glass bone, such as the compressive strength, the fracture toughness and the like, can form a cross structure while stabilizing the structure, and is favorable for bone seed cell adhesion and host blood vessel ingrowth.
Further, the above-mentioned Na2O-CaO-SiO2-P2O5The system takes 25-85 parts by weight of sodium citrate, 10-50 parts by weight of calcium carbonate, 140-210 parts by weight of tetraethyl orthosilicate and 4-16 parts by weight of tricalcium phosphate as initial formula components, and the sodium citrate and the calcium carbonate in the formula are decomposed in a heat treatment link, are raw materials, have the function of a pore-forming agent and can form uniform small pores matched with three-dimensional network-shaped large pores.
Further, the reinforcing phase is Ca1-δMgδSi2O2N2(delta is more than or equal to 0.05 and less than or equal to 0.08), excessive magnesium doping can cause that a stable reinforcing phase with a proper morphology can not be generated, too little magnesium doping can influence the degradation condition of the material, and when delta is 0.05-0.08, the comprehensive performance is optimal.
Further, the above Ca1-δMgδSi2O2N2(delta is not less than 0.01 but not more than 0.1) is Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 10-20%, so that the mechanical property of the glass bone can be obviously enhanced; too small an amount of addition cannot be usedThe rod-shaped structures are crossed with each other, the advantages of the rod-shaped structures are reflected, and the degradation characteristic of the whole bioglass is influenced by excessive addition amount.
Further, the above Ca1-δMgδSi2O2N2The raw material is CaCO3、MgCO3、α-Si3N4Amorphous SiO2The carbon fiber-based composite material is prepared by sintering and crushing carbon fibers serving as a raw material and serving as a template at 1200-1400 ℃ in a nitrogen atmosphere, and the preparation process comprises the following steps:
firstly, weighing CaCO in stoichiometric ratio within the allowable error range3、MgCO3、α-Si3N4Amorphous SiO2Adding 10-40% by mass of the above substances of short carbon fibers with diameter of 1-5 μm and length of 0.2-0.5 mm, adding a solvent to form a slurry, adjusting pH to 10 with ammonia water, and performing wet ball milling and mixing;
secondly, drying and crushing the mixed slurry to form a precursor;
thirdly, sintering the precursor for 2-4h at 1200-1400 ℃ in nitrogen atmosphere, crushing, sieving and collecting.
Further, the above Ca1-δMgδSi2O2N2The mesh number of (2) is 800-2000 meshes, the sintering performance and the degradation characteristic of the whole bioglass can be influenced by excessively large particles, and the mechanical reinforcing effect of excessively small particles is poor.
Further, the amount of the above-mentioned polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer added is Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 50-100%, and the addition amount of the soft template directly influences the formation of three-dimensional pore channels and the improvement of mechanical properties.
Further, the preparation method of the reinforced bioglass bone repair material is characterized by comprising the following steps:
weighing sodium citrate, calcium carbonate, tetraethyl orthosilicate, tricalcium phosphate, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and Ca according to proportion1-δMgδSi2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
step two, stirring and concentrating the slurry at the temperature of 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank;
and step three, carrying out heat treatment on the blank body for 2-4H in an oxidizing atmosphere at the temperature of 1000-1100 ℃ to obtain a product.
Further, the oxidizing atmosphere is air, sodium citrate and calcium carbonate are decomposed when the material is sintered at high temperature in the air, the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer template and the carbon fiber are oxidized, and the generated CO gas has certain reducibility and can promote Ca1-δMgδSi2O2N2The nitrogen-containing structure can enter the system without being oxidized, and the atmosphere environment with too strong oxidizing property is easy to cause the loss of nitrogen content.
The invention has the following beneficial effects:
the invention adds (Ca, Mg) Si with the length-diameter ratio of 10: 1-20: 12O2N2The reinforcing phase has a short rod-shaped structure, can be mutually crossed in a bioglass system, and can keep the integral characteristics of bioglass and obviously improve the mechanical strength under the synergistic action of other components; the invention forms a three-dimensional through large pore canal with better distribution by a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer soft template method, sodium citrate and calcium carbonate are decomposed to form small pores, carbon fiber is decomposed to form a middle pore, and the three pores with different sizes are matched, so that the mechanical strength is improved, and meanwhile, the pore canal necessary for bone growth is provided; (Ca, Mg) Si of the present invention2O2N2The carbon fiber template in the reinforcing phase is oxidized and eliminated from the system when the bioglass material is formed, so that (Ca, Mg) Si2O2N2The enhancement of the degradation properties with respect to bioglass has no significant effect.
[ description of the drawings ]
Ca obtained when δ is 0.05 and 0.08 in FIG. 11-δMgδSi2O2N2An XRD pattern of (a);
FIG. 2 shows Ca obtained by using chopped carbon fibers as a template1-δMgδSi2O2N2SEM picture of (1);
FIG. 3 is a schematic diagram of the internal structure of a rectangular parallelepiped glass skeleton material, wherein (a), (b) and (c) are SEM pictures of glass skeleton cross sections, and (d), (e) and (f) are glass skeleton Micro-CT.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples. The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution, and the directions described are limited to the drawings. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
The preparation method of the reinforced bioglass bone repair material is characterized in that bioglass bone is Na2O-CaO-SiO2-P2O5The system is prepared by taking a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer as a template and Ca with the length-diameter ratio of 10: 1-20: 11-δMgδSi2O2N2(delta is more than or equal to 0.01 and less than or equal to 0.1) is taken as a reinforcing phase. The polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymer is an amphiphilic molecule, forms multi-molecule aggregated micelles in aqueous solution spontaneously, has good dispersibility, can realize self-assembly with hydrogen bonds existing in large amount in tetraethyl orthosilicate (TEOS) in mixed slurry, and can generate three-dimensional network-shaped large pore canals after a template agent is removed at high temperature. Rod-shaped CaSi2O2N2Is a nitrogen-containing crystalline phase (P)21) By small amounts of Mg2+Substituted Ca2+The delta is preferably 0.01-0.1, and further preferably 0.05-0.08, so that rod-shaped grains can be generated, the mechanical strength such as the compressive strength and the fracture toughness of the glass bone can be effectively improved, a cross structure is formed while the structure is stabilized, and the adhesion of bone seed cells and the ingrowth of host blood vessels are facilitated.
Na2O-CaO-SiO2-P2O5The system takes 25-85 parts by weight of sodium citrate, 10-50 parts by weight of calcium carbonate, 140-210 parts by weight of tetraethyl orthosilicate and 4-16 parts by weight of tricalcium phosphate as initial formula components, the sodium citrate and the calcium carbonate in the formula are decomposed in a heat treatment link, are raw materials, have the function of a pore-forming agent, can form uniform small pores matched with three-dimensional network-shaped large pores, are beneficial to removal of a template in a synthesis process, and have better safety in a dispersion process.
The addition amount of the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer is Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 50-100%, and the addition amount of the soft template directly influences the formation of three-dimensional pore channels and the improvement of mechanical properties.
In the silicon oxynitride compound, the types and contents of metal ions are directly related to properties such as phases, shapes and stability, and Ca is used1-δMgδSi2O2N2(delta is more than or equal to 0.05 and less than or equal to 0.08) is a reinforcing phase of the glass bone, excessive magnesium doping can cause that a stable rod-shaped structure with a proper length-diameter ratio cannot be generated, the reinforcing effect of the rod-shaped structure is obviously better than that of other structures, too little magnesium doping can influence the degradation condition of the material, and when delta is 0.05-0.08, the comprehensive performance is optimal. Ca1-δMgδSi2O2N2(delta is not less than 0.01 but not more than 0.1) is Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 10-20%, and the mechanical property of the glass bone can be obviously enhanced. Ca1-δMgδSi2O2N2From CaCO3、MgCO3、α-Si3N4Amorphous SiO2Sintering at 1200-1400 ℃ in nitrogen atmosphere and then crushing. Ca obtained when δ is 0.05 and 0.08 in FIG. 11-δMgδSi2O2N2XRD pattern of (a).
Ca1-δMgδSi2O2N2The raw material is CaCO3、MgCO3、α-Si3N4Amorphous SiO2The carbon fiber-based composite material is prepared by sintering and crushing carbon fibers serving as a raw material and serving as a template at 1200-1400 ℃ in a nitrogen atmosphere, and the preparation process comprises the following steps:
firstly, weighing CaCO in stoichiometric ratio within the allowable error range3、MgCO3、α-Si3N4Amorphous SiO2Adding 10-40% by mass of the above substances of short carbon fibers with diameter of 1-5 μm and length of 0.2-0.5 mm, adding a solvent to form a slurry, adjusting pH to 10 with ammonia water, and performing wet ball milling and mixing;
secondly, drying and crushing the mixed slurry to form a precursor;
thirdly, sintering the precursor at 1200-1400 ℃ for 2-4h in nitrogen atmosphere, crushing, sieving, and collecting 800-2000-mesh particles as a reinforcing phase, wherein oversized particles can influence the sintering performance and degradation characteristics of the whole bioglass, and undersized particles have poor mechanical reinforcing effect; in the nitrogen environment, the carbon fiber still remains inside the crystal grains, and the morphology is shown in fig. 2. The carbon content is detected, and the retention rate is over 90 percent.
Further, the preparation method of the reinforced bioglass bone repair material is characterized by comprising the following steps:
weighing sodium citrate, calcium carbonate, tetraethyl orthosilicate, tricalcium phosphate, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and Ca according to proportion1-δMgδSi2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
step two, stirring and concentrating the slurry at the temperature of 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank;
and step three, carrying out heat treatment on the blank body for 2-4H in an oxidizing atmosphere at the temperature of 1000-1100 ℃ to obtain a product.
Further, the oxidizing atmosphere is air, and when the sodium citrate and the calcium carbonate are sintered at high temperature in the air, the sodium citrate and the calcium carbonate are decomposed, and the polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymerThe polymer template and the carbon fiber are oxidized, and the generated CO gas has certain reducibility and can promote Ca1-δMgδSi2O2N2The nitrogen-containing structure can enter the system without being oxidized, and the atmosphere environment with too strong oxidizing property is easy to cause the loss of nitrogen content.
For porous materials, when loaded, microcracks first develop at the grain junctions, and then the microcracks join the pores and allow the cracks to grow rapidly, so the compressive strength of the material depends primarily on the bond strength between the grains and the pore characteristics. According to Griffith microcrack theory, the strength of a material does not depend on the number of cracks, but on the size of the cracks, which rapidly propagate to fracture the material once they exceed a critical size. The reinforced bioglass bone repair material of the invention has three sizes of pores: forming three-dimensional through large pore channels by using a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer soft template method, forming middle pores by decomposing carbon fibers, and forming small pores by decomposing sodium citrate and calcium carbonate; the cooperation of a plurality of pores not only provides the space required by the production of osteocytes and the attachment of active substances, but also is beneficial to the mechanical performance of the whole structure.
FIG. 3 is a schematic diagram of the internal structure of a rectangular parallelepiped glass skeleton material, wherein (a), (b) and (c) are SEM pictures of glass skeleton cross sections, and (d), (e) and (f) are glass skeleton Micro-CT.
Example one
A preparation method of a reinforced bioglass bone repair material comprises the following specific steps:
1) 90g of CaCO are weighed3、8.4g MgCO3、70.14gα-Si3N430.05g of amorphous SiO2Grinding and mixing, adding 20g of short carbon fibers with the diameter of 1 mu m and the length of 0.2mm, adding a solvent to form slurry, adjusting the pH value to 10 by using ammonia water, and performing wet ball milling and mixing;
2) drying and crushing the mixed slurry, and sieving the crushed slurry with a sieve of 800 meshes to form a precursor;
3) sintering the precursor at 1200-1400 ℃ for 2-4h in a nitrogen atmosphere, crushing, sieving, and collecting 800-2000-mesh particles; through detection, the length-diameter ratio of the particles is about 10: 1-20: 1, and the particles are bondedThe crystal phase is monoclinic Ca0.9Mg0.1Si2O2N2；
4) 25g of sodium citrate, 10g of calcium carbonate, 140g of tetraethyl orthosilicate, 4g of tricalcium phosphate, 90g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and 18g of Ca are weighed0.9Mg0.1Si2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
5) stirring and concentrating the slurry at 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank with the length, the width and the height of 35 multiplied by 8 mm;
6) and (3) carrying out heat treatment on the blank body for 2-4h in an oxidizing atmosphere at 1000-1100 ℃ to obtain the final product reinforced glass bone material.
The porosity of the reinforced glass bone material is 72 percent, the compressive strength is 8.6 +/-1 MPa, and the fracture toughness is 1.82 +/-0.05 MPa1/2The carbon content was 0.2% and the nitrogen content was 2.5%.
Example two
A preparation method of a reinforced bioglass bone repair material comprises the following specific steps:
1) weighing 99g of CaCO3、0.84g MgCO3、70.14gα-Si3N430.05g of amorphous SiO2Grinding and mixing, adding 40g of short carbon fibers with the diameter of 5 mu m and the length of 0.5mm, adding a solvent to form slurry, adjusting the pH value to 10 by using ammonia water, and performing wet ball milling and mixing;
2) drying and crushing the mixed slurry, and sieving the crushed slurry with a sieve of 800 meshes to form a precursor;
3) sintering the precursor at 1200-1400 ℃ for 2-4h in a nitrogen atmosphere, crushing, sieving, and collecting 800-2000-mesh particles; the detection shows that the length-diameter ratio of the particles is about 10: 1-20: 1, and the crystal phase is monoclinic Ca0.99Mg0.01Si2O2N2；
4) 42.5g of sodium citrate, 25g of calcium carbonate, 155g of tetraethyl orthosilicate, 8g of tricalcium phosphate, 230.5g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and 46g of Ca are weighed0.99Mg0.01Si2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
5) stirring and concentrating the slurry at 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank with the length, the width and the height of 35 multiplied by 8 mm;
6) and (3) carrying out heat treatment on the blank body for 2-4h in an oxidizing atmosphere at 1000-1100 ℃ to obtain the final product reinforced glass bone material.
The porosity of the reinforced glass bone material is 76%, the compressive strength is 7.9 +/-1 MPa, and the fracture toughness is 1.80 +/-0.05 MPa1/2The carbon content was 0.3% and the nitrogen content was 3.1%.
EXAMPLE III
A preparation method of a reinforced bioglass bone repair material comprises the following specific steps:
1) 95g of CaCO are weighed3、4.2g MgCO3、70.14gα-Si3N430.05g of amorphous SiO2Grinding and mixing, adding 60g of chopped carbon fibers with the diameter of 2 mu m and the length of 0.25mm, adding a solvent to form slurry, adjusting the pH value to 10 by using ammonia water, and performing wet ball milling and mixing;
2) drying and crushing the mixed slurry, and sieving the crushed slurry with a sieve of 800 meshes to form a precursor;
3) sintering the precursor at 1200-1400 ℃ for 2-4h in a nitrogen atmosphere, crushing, sieving, and collecting 800-2000-mesh particles; the detection shows that the length-diameter ratio of the particles is about 10: 1-20: 1, and the crystal phase is monoclinic Ca0.95Mg0.05Si2O2N2；
4) 95g of sodium citrate, 30g of calcium carbonate, 160g of tetraethyl orthosilicate, 10g of tricalcium phosphate, 200g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and 40g of Ca are weighed0.95Mg0.05Si2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
5) stirring and concentrating the slurry at 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank with the length, the width and the height of 35 multiplied by 8 mm;
6) and (3) carrying out heat treatment on the blank body for 2-4h in an oxidizing atmosphere at 1000-1100 ℃ to obtain the final product reinforced glass bone material.
The porosity of the reinforced glass bone material is 77%, the compressive strength is 7.5 +/-1 MPa, and the fracture toughness is 1.75 +/-0.05 MPa1/2The carbon content was 0.3% and the nitrogen content was 2.8%.
Example four
A preparation method of a reinforced bioglass bone repair material comprises the following specific steps:
1) 92g of CaCO are weighed3、6.72g MgCO3、70.14gα-Si3N430.05g of amorphous SiO2Grinding and mixing, adding 80g of short carbon fibers with the diameter of 4 mu m and the length of 0.4mm, adding a solvent to form slurry, adjusting the pH value to 10 by using ammonia water, and performing wet ball milling and mixing;
2) drying and crushing the mixed slurry, and sieving the crushed slurry with a sieve of 800 meshes to form a precursor;
3) sintering the precursor at 1200-1400 ℃ for 2-4h in a nitrogen atmosphere, crushing, sieving, and collecting 800-2000-mesh particles; the length-diameter ratio of the particles is about 10: 1-20: 1 through SEM detection, and XRD results show that the particles are monoclinic Ca0.92Mg0.08Si2O2N2；
4)60g of sodium citrate, 35g of calcium carbonate, 180g of tetraethyl orthosilicate, 12g of tricalcium phosphate, 200g of polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and 18g of Ca0.92Mg0.08Si2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
5) stirring and concentrating the slurry at 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank with the length, the width and the height of 35 multiplied by 8 mm;
6) and (3) carrying out heat treatment on the blank body for 2-4h in an oxidizing atmosphere at 1000-1100 ℃ to obtain the final product reinforced glass bone material.
The porosity of the reinforced glass bone material is 70 percent, the compressive strength is 9.5 +/-1 MPa, and the fracture toughness is 1.88 +/-0.05 MPa1/2,The carbon content was 0.2% and the nitrogen content was 3.5%.

Claims (9)

1. The preparation method of the reinforced bioglass bone repair material is characterized in that bioglass bone is Na2O-CaO-SiO2-P2O5The system is prepared by taking a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer as a template and Ca with the length-diameter ratio of 10: 1-20: 11-δMgδSi2O2N2Is a reinforcing phase, wherein delta is more than or equal to 0.01 and less than or equal to 0.1; the preparation method comprises the following steps:
weighing sodium citrate, calcium carbonate, tetraethyl orthosilicate, tricalcium phosphate, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and Ca according to proportion1-δMgδSi2O2N2Adding water into raw materials to prepare mixed slurry with the solid content of 55-65%;
step two, stirring and concentrating the slurry at the temperature of 80 ℃ to form a pug with the water content of 2-3%, and carrying out compression molding to form a blank;
and step three, carrying out heat treatment on the blank body for 2-4h at the temperature of 1000-1100 ℃ in an oxidizing atmosphere to obtain a product.
2. The method of claim 1, wherein the Na is selected from the group consisting of sodium, potassium, sodium, potassium, magnesium, sodium, potassium, magnesium, sodium, potassium, sodium, potassium, magnesium, sodium, magnesium, and magnesium2O-CaO-SiO2-P2O5The system takes 25-85 parts by weight of sodium citrate, 10-50 parts by weight of calcium carbonate, 140-210 parts by weight of tetraethyl orthosilicate and 4-16 parts by weight of tricalcium phosphate as initial formula components.
3. The method for preparing a reinforced bioglass bone repair material as claimed in claim 1, wherein the reinforcing phase Ca1-δMgδSi2O2N2Delta of (d) is 0.05 to 0.08.
4. The method of claim 1, wherein the Ca is selected from the group consisting of Ca, and Ca1-δMgδSi2O2N2In an amount of Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 10-20 percent.
5. The method of claim 1, wherein the Ca is selected from the group consisting of Ca, and Ca1-δMgδSi2O2N2The raw material is CaCO3、MgCO3、α-Si3N4Amorphous SiO2The carbon fiber is used as a raw material, carbon fiber is used as a template, and the carbon fiber is obtained by sintering and crushing at 1200-1400 ℃ in a nitrogen atmosphere.
6. The method for preparing a reinforced bioglass bone repair material as claimed in claim 5, wherein the Ca is1-δMgδSi2O2N2The preparation process is as follows:
firstly, weighing CaCO in stoichiometric ratio within the allowable error range3、MgCO3、α-Si3N4Amorphous SiO2Adding 10-40% by mass of the above substances of short carbon fibers with diameter of 1-5 μm and length of 0.2-0.5 mm, adding a solvent to form a slurry, adjusting pH to 10 with ammonia water, and performing wet ball milling and mixing;
secondly, drying and crushing the mixed slurry to form a precursor;
thirdly, sintering the precursor at 1200-1400 ℃ for 2-4h in nitrogen atmosphere, crushing, sieving and collecting.
7. The method of claim 6, wherein the Ca is selected from the group consisting of Ca, and Ca1-δMgδSi2O2N2The mesh number of the sieve is 800-2000 meshes.
8. The method for preparing a reinforced bioglass bone repair material as in claim 1, wherein said polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer is added in an amount that is sufficient to provide a bone repair material that is substantially free of said polyoxyethylene-polyoxypropylene triblock copolymerIs Na2O-CaO-SiO2-P2O5The total weight of the initial formula components of the system is 50-100 percent.
9. The method of claim 1, wherein the oxidizing atmosphere is air.
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