技术领域technical field
本发明属于医用生物材料领域，涉及一种具有抗溃散性能的钙硅基复合骨水泥材料及其制备方法和应用。该可注射性材料作为人体硬组织填充修复材料，可用于牙科、骨科等用途。The invention belongs to the field of medical biomaterials, and relates to a calcium-silica-based composite bone cement material with anti-collapse performance, a preparation method and application thereof. The injectable material can be used as a human hard tissue filling and repairing material, and can be used in dentistry, orthopedics and the like.
背景技术Background technique
骨缺损是骨科中最常见的疾病，需要大量的骨修复材料来治愈和修复，因此研制各种适合于人体骨缺损修复的生物医用材料具有重要的社会意义。在无机骨修复材料领域，相比于块状的生物陶瓷材料，自固化材料因其具有低温固化、可注射、可根据骨缺损部位的形状任意塑形的独特性能(Journal of the Ceramic Society of Japan1991；99:954-64)得到广泛的关注及应用。Bone defect is the most common disease in orthopedics, and a large number of bone repair materials are needed to heal and repair. Therefore, it is of great social significance to develop various biomedical materials suitable for human bone defect repair. In the field of inorganic bone repair materials, compared with bulk bioceramic materials, self-curing materials have the unique properties of low-temperature curing, injectability, and arbitrarily shaping according to the shape of bone defects (Journal of the Ceramic Society of Japan1991 ;99:954-64) has received extensive attention and application.
目前，临床应用上的无机骨水泥主要包括硫酸钙(Calcium Sulfate Cement,CSC)(Journal of Inorganic Materials2013；28:795-803)、磷酸钙(Calcium PhosphateCement,CPC)(Journal of Applied Biomaterials&Functional Materials 2012；10:2-11)等，但是传统的骨水泥存在缺乏生物活性(Journal of Materials Science-Materialsin Medicine2013；24:355-64)、降解速度和骨生成速度不匹配(Acta Biomaterialia2014；10:3279-87；Journal of Spinal Disorders&Techniques 2012；25:333-7)等问题。因此，研制开发新型骨水泥体系具有十分重要的意义。研究表明，以硅酸三钙(Ca3SiO5)(Journal of Biomedical Materials Research Part A2008；85A:336-44)、硅酸二钙(Ca2SiO4)(Journal of Biomedical Materials Research Part B-Applied Biomaterials2005；73B:244-51)为代表的新型钙硅基骨水泥与水调和后形成的水泥浆体具有自行固化、任意塑形的特点，并且该体系骨水泥具有良好的生物活性和降解性，在降解过程中溶出的硅离子能促进成骨细胞增殖和分化(Journal of Materials Chemistry2009；19:1183；Journal of Dentistry 2014；42:517-33)。但是，钙硅基骨水泥存在抗溃散性差、凝固时间长、力学强度偏低等一系列的问题，并且在注射过程中会产生严重的固液分离现象。Liu等人(International Journal of Applied Ceramic Technology 2011；8:560-565)将硅酸三钙(C3S)、硅酸二钙(C2S)两种粉体复合，通过调控两种粉体的比例对骨水泥的理化性能进行一系列的调控，并且能够有效缩短骨水泥的凝固时间、提高骨水泥的抗压强度。然而这些工作仍无法克服钙硅基骨水泥固有的缺点，这将导致骨水泥在应用中容易被血液冲散，在注射过程中产生严重的固液分离等问题。因此，研制一种既具有生物活性又具有优异的抗溃散性、可注射/可塑形的新型骨水泥是十分必要的。At present, the clinically applied inorganic bone cement mainly includes calcium sulfate (Calcium Sulfate Cement, CSC) (Journal of Inorganic Materials 2013; 28:795-803), calcium phosphate (Calcium Phosphate Cement, CPC) (Journal of Applied Biomaterials & Functional Materials 2012; 10 :2-11), etc., but the traditional bone cement lacks biological activity (Journal of Materials Science-Materials in Medicine2013; 24:355-64), and the degradation rate does not match the bone formation rate (Acta Biomaterialia2014; 10:3279-87; Journal of Spinal Disorders&Techniques 2012; 25:333-7) and other issues. Therefore, it is of great significance to research and develop new bone cement systems. Studies have shown that tricalcium silicate (Ca3 SiO5 ) (Journal of Biomedical Materials Research Part A2008; 85A:336-44), dicalcium silicate (Ca2 SiO4 ) (Journal of Biomedical Materials Research Part B-Applied Biomaterials2005; 73B:244-51) represents the new type of calcium-silica-based bone cement and water to form a cement paste that has the characteristics of self-curing and arbitrary shaping, and the bone cement of this system has good bioactivity and degradability. The silicon ions released during the degradation process can promote the proliferation and differentiation of osteoblasts (Journal of Materials Chemistry 2009; 19:1183; Journal of Dentistry 2014; 42:517-33). However, calcium-silica-based bone cement has a series of problems such as poor collapse resistance, long setting time, and low mechanical strength, and serious solid-liquid separation will occur during the injection process. Liu et al. (International Journal of Applied Ceramic Technology 2011; 8:560-565) combined tricalcium silicate (C3 S) and dicalcium silicate (C2 S) powders, and adjusted the two powders The proportion of the bone cement can be adjusted in a series of physical and chemical properties, and can effectively shorten the setting time of the bone cement and improve the compressive strength of the bone cement. However, these works still cannot overcome the inherent shortcomings of calcium-silica-based bone cement, which will lead to bone cement being easily washed away by blood during application, and severe solid-liquid separation during injection. Therefore, it is very necessary to develop a new type of bone cement that has both biological activity and excellent collapse resistance, and is injectable/shapeable.
发明内容Contents of the invention
针对现有技术的以上缺陷，本发明的目的在于提供一种具有抗溃散特性的的钙硅基复合骨水泥。其中钙硅基骨水泥能够自行固化，并且该体系骨水泥具有良好的生物活性和降解性，在降解过程中溶出的硅(Si)离子能促进成骨细胞增殖和分化；海藻酸钠(SA)会同钙(Ca)离子反应生成海藻酸钙水凝胶，有效抑制了钙硅基骨水泥的溃散。In view of the above defects of the prior art, the object of the present invention is to provide a calcium-silica-based composite bone cement with anti-collapse properties. Among them, the calcium-silica-based bone cement can solidify by itself, and the bone cement of this system has good bioactivity and degradability, and the silicon (Si) ions dissolved during the degradation process can promote the proliferation and differentiation of osteoblasts; sodium alginate (SA) It will react with calcium (Ca) ions to form calcium alginate hydrogel, which effectively inhibits the collapse of calcium-silica-based bone cement.
在此，本发明提供一种抗溃散钙硅基复合骨水泥，所述钙硅基复合骨水泥由固相原料与液相原料按照液固比为0.4～1.2mL/g的比例调和得到，其中，所述固相原料为钙硅基材料，所述液相原料为海藻酸钠溶液。Here, the present invention provides an anti-collapse calcium-silica-based composite bone cement, which is obtained by blending solid-phase raw materials and liquid-phase raw materials according to a liquid-solid ratio of 0.4-1.2mL/g, wherein , the solid-phase raw material is a calcium-silicon-based material, and the liquid-phase raw material is a sodium alginate solution.
该材料是以具有生物活性的钙硅基骨水泥粉体为固相组成，以海藻酸钠(Sodiumalginate，SA)溶液为调和液，经调和均匀后形成。本发明利用钙硅基骨水泥和海藻酸钠的特性，制备出新型的可注射的钙硅基生物活性骨水泥，制备方法简单。该复合骨水泥材料具有优异的可注射性、可塑性及抗溃散性，适用于牙科、骨科等用途。其可注射性、可塑形性、凝固时间和力学强度等性能可以通过调节组成进行调控。此外，复合材料还具有良好的生物活性和可调控的降解性能，并且能够支持相关成骨细胞的增殖和分化。本发明具有制备工艺简单易行、成本低廉、易规模化制备等优点。The material is composed of biologically active calcium-silica-based bone cement powder as a solid phase, and a sodium alginate (Sodiumalginate, SA) solution as a blending liquid, which is formed after uniform blending. The invention utilizes the properties of the calcium-silicon-based bone cement and sodium alginate to prepare a novel injectable calcium-silicon-based bioactive bone cement, and the preparation method is simple. The composite bone cement material has excellent injectability, plasticity and collapse resistance, and is suitable for use in dentistry, orthopedics and the like. Its properties such as injectability, plasticity, solidification time and mechanical strength can be adjusted by adjusting the composition. In addition, the composite material also has good bioactivity and tunable degradation performance, and can support the proliferation and differentiation of related osteoblasts. The invention has the advantages of simple and easy preparation process, low cost, easy large-scale preparation and the like.
较佳地，所述钙硅基材料的组成为：硅酸三钙(Ca3SiO5，C3S)、硅酸二钙(Ca2SiO4，C2S)或硅酸三钙/硅酸二钙(Ca3SiO5/Ca2SiO4，C3S/C2S)混合粉体，钙硅基混合粉体中硅酸三钙(C3S)粉体的含量为0～100％，硅酸二钙(C2S)粉体的含量为0～100％。Preferably, the composition of the calcium-silicon-based material is: tricalcium silicate (Ca3 SiO5 , C3 S), dicalcium silicate (Ca2 SiO4 , C2 S) or tricalcium silicate/silicon Dicalcium silicate (Ca3 SiO5 /Ca2 SiO4 , C3 S/C2 S) mixed powder, the content of tricalcium silicate (C3 S) powder in the calcium-silicon based mixed powder is 0-100 %, the content of dicalcium silicate (C2 S) powder is 0-100%.
较佳地，硅酸三钙粉体的粒径为1～100μm，硅酸二钙粉体粒径为1～100μm。Preferably, the particle size of the tricalcium silicate powder is 1-100 μm, and the particle size of the dicalcium silicate powder is 1-100 μm.
较佳地，所述海藻酸钠溶液为海藻酸钠水溶液，浓度为0.1wt％～10wt％。Preferably, the sodium alginate solution is an aqueous solution of sodium alginate with a concentration of 0.1wt%-10wt%.
较佳地，海藻酸钠的分子量为5000～200000。Preferably, the molecular weight of sodium alginate is 5,000-200,000.
本发明的钙硅基复合骨水泥具有以下一个或多个特征：The calcium-silica-based composite bone cement of the present invention has one or more of the following characteristics:
抗溃散性能：注入水中不发生溃散(将复合骨水泥浆体注入去离子水中，未有溃散现象发生)，置于120r/分钟震荡24小时后，复合骨水泥浆体的失重率小于5％；Anti-collapse performance: no collapse occurs when injected into water (the composite bone cement slurry is injected into deionized water, no collapse occurs), and after being placed in 120r/min for 24 hours, the weight loss rate of the composite bone cement slurry is less than 5%;
凝固时间：初凝时间为20～80分钟，终凝时间为30～180分钟；Setting time: the initial setting time is 20-80 minutes, and the final setting time is 30-180 minutes;
可注射性能：静置5～30分钟后可注射率为90～100％；Injectable performance: After standing for 5-30 minutes, the injectable rate is 90-100%;
抗压强度:养护28天后，抗压强度大于20MPa，优选20～60MPa，更优选50MPa以上。Compressive strength: after curing for 28 days, the compressive strength is greater than 20MPa, preferably 20-60MPa, more preferably above 50MPa.
本发明的另一目的在于提供一种钙硅基复合骨水泥的制备方法，其特征在于，所述制备方法包括：将钙硅基材料粉体与海藻酸钠溶液按照液固比为0.4～1.2mL/g的比例调和，得到具有抗溃散性质的钙硅基/海藻酸钠复合骨水泥。Another object of the present invention is to provide a preparation method of calcium-silicon-based composite bone cement, which is characterized in that the preparation method comprises: mixing calcium-silicon-based material powder and sodium alginate solution at a liquid-solid ratio of 0.4 to 1.2 The ratio of mL/g was adjusted to obtain a calcium-silica-based/sodium alginate composite bone cement with anti-collapse properties.
较佳地，所述海藻酸钠溶液由海藻酸钠粉体加入水中，搅拌1～5小时配制得到，所述海藻酸钠溶液的浓度为0.1wt％～10wt％，海藻酸钠的分子量为5000～200000。Preferably, the sodium alginate solution is prepared by adding sodium alginate powder into water and stirring for 1 to 5 hours, the concentration of the sodium alginate solution is 0.1 wt% to 10 wt%, and the molecular weight of sodium alginate is 5000 ~200000.
较佳地，所述钙硅基材料粉体为硅酸三钙、硅酸二钙或硅酸三钙/硅酸二钙混合粉体，其中，硅酸三钙粉体的粒径为1～100μm，硅酸二钙粉体粒径为1～100μm。Preferably, the calcium-silicon-based material powder is tricalcium silicate, dicalcium silicate or tricalcium silicate/dicalcium silicate mixed powder, wherein the particle size of the tricalcium silicate powder is 1- 100 μm, the particle size of dicalcium silicate powder is 1-100 μm.
本发明的目的还在于提供上述钙硅基复合骨水泥在制备用于微创治疗或复杂骨缺损形状的填充的材料中的应用。该复合骨水泥材料具有优异的抗溃散性、可注射性或可塑性，适用于牙科、骨科等用途。The purpose of the present invention is also to provide the application of the above-mentioned calcium-silica-based composite bone cement in the preparation of materials for minimally invasive treatment or filling of complex bone defect shapes. The composite bone cement material has excellent collapse resistance, injectability or plasticity, and is suitable for use in dentistry, orthopedics and the like.
附图说明Description of drawings
图1为钙硅基/海藻酸钠复合骨水泥养护14天后的XRD图谱(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。(a)硅酸三钙；(b)调和液为1.0％海藻酸钠溶液；(c)调和液为1.5％海藻酸钠溶液；(d)调和液为2.0％海藻酸钠溶液(◆：C-S-H；*：C3S；O：Ca(OH)2)。Figure 1 is the XRD pattern of the calcium-silica-based/sodium alginate composite bone cement after 14 days of curing (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g). (a) tricalcium silicate; (b) the blending solution is 1.0% sodium alginate solution; (c) the blending liquid is 1.5% sodium alginate solution; (d) the blending liquid is 2.0% sodium alginate solution (◆: CSH ;*: C3 S; O: Ca(OH)2 ).
图2为钙硅基/海藻酸钠复合骨水泥养护14天后的断面形貌图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。(a)硅酸三钙；(b)调和液为1.0％海藻酸钠溶液；(c)调和液为1.5％海藻酸钠溶液；(d)调和液为2.0％海藻酸钠溶液。Figure 2 is the cross-sectional morphology of the calcium-silica-based/sodium alginate composite bone cement after 14 days of curing (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g). (a) tricalcium silicate; (b) the blending liquid is 1.0% sodium alginate solution; (c) the blending liquid is 1.5% sodium alginate solution; (d) the blending liquid is 2.0% sodium alginate solution.
图3为钙硅基/海藻酸钠复合骨水泥的抗溃散性比较图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。(a)硅酸三钙；(b)调和液为1.0％海藻酸钠溶液；(c)调和液为1.5％海藻酸钠溶液；(d)调和液为2.0％海藻酸钠溶液。Figure 3 is a comparison chart of the collapse resistance of calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g). (a) tricalcium silicate; (b) the blending liquid is 1.0% sodium alginate solution; (c) the blending liquid is 1.5% sodium alginate solution; (d) the blending liquid is 2.0% sodium alginate solution.
图4为钙硅基/海藻酸钠复合骨水泥的可注射性比较图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Figure 4 is a comparison chart of injectability of calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g).
图5为钙硅基/海藻酸钠复合骨水泥的可塑性图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Figure 5 is the plasticity diagram of calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g).
图6为钙硅基/海藻酸钠复合骨水泥的固化时间图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Fig. 6 is the solidification time diagram of the calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6 mL/g).
图7为钙硅基/海藻酸钠复合骨水泥的抗压强度图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Figure 7 is a diagram of the compressive strength of calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g).
图8为钙硅基/海藻酸钠复合骨水泥在SBF中浸泡14天后表面形貌及EDS图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。(a)硅酸三钙；(b)调和液为1.5％海藻酸钠溶液。Figure 8 is the surface morphology and EDS image of the calcium-silica-based/sodium alginate composite bone cement soaked in SBF for 14 days (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g) . (a) tricalcium silicate; (b) the blending liquid is 1.5% sodium alginate solution.
图9为钙硅基/海藻酸钠复合骨水泥的降解性图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Figure 9 is a diagram of the degradability of calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6mL/g).
图10为钙硅基/海藻酸钠复合骨水泥的的细胞相容性图(本图中钙硅基材料为硅酸三钙粉体，液固比为0.6mL/g)。Fig. 10 is the cytocompatibility diagram of the calcium-silica-based/sodium alginate composite bone cement (the calcium-silica-based material in this figure is tricalcium silicate powder, and the liquid-solid ratio is 0.6 mL/g).
具体实施方式Detailed ways
以下结合附图和下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below in conjunction with the accompanying drawings and the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, not to limit the present invention.
本发明中，以具有生物活性的钙硅基骨水泥为基础，向其中引入生物相容性优异的高分子，最终希望获得抗溃散性、可注射性优异或可任意塑形的复合骨水泥浆体。本发明中选用的高分子为海藻酸钠(SA)，原因在于天然高分子海藻酸钠(SA)具有持水性、低毒性、生物相容性、螯合性等特点，在伤口敷料、药物及细胞载体等方面得到广泛的应用(Progress in Polymer Science 2012；37:106-2)。海藻酸钠(SA)会和钙(Ca)离子发生螯合反应生成具有抗溃散性的海藻酸钙水凝胶，而钙硅基骨水泥成分在水化形成C-S-H网络结构的过程中会不断释放钙(Ca)离子。因此我们基于钙硅基骨水泥在水化过程中释放钙(Ca)离子的特性，将其与海藻酸钠(SA)的特性相结合，形成具有抗溃散性的新型钙硅基复合骨水泥。In the present invention, on the basis of bioactive calcium-silica-based bone cement, polymers with excellent biocompatibility are introduced into it, and finally it is hoped to obtain a composite bone cement slurry with excellent collapse resistance, excellent injectability or arbitrary shape body. The macromolecule selected in the present invention is sodium alginate (SA), and reason is that natural macromolecular sodium alginate (SA) has characteristics such as water holding capacity, low toxicity, biocompatibility, chelating property, in wound dressing, medicine and Cell carriers have been widely used (Progress in Polymer Science 2012; 37:106-2). Sodium alginate (SA) will undergo a chelation reaction with calcium (Ca) ions to form an anti-collapse calcium alginate hydrogel, and the calcium-silica-based bone cement components will be continuously released during the process of hydration to form a C-S-H network structure Calcium (Ca) ions. Therefore, based on the characteristics of calcium-silica-based bone cement releasing calcium (Ca) ions during hydration, we combined it with the properties of sodium alginate (SA) to form a new type of calcium-silica-based composite bone cement with anti-collapse properties.
本发明的抗溃散钙硅基复合骨水泥材料，固相原料为具有自固化性能的钙硅基材料，液相原料为海藻酸钠(SA)溶液，二者经均匀调制混合后，形成具有抗溃散性能、可注射或可塑形的自固化骨水泥浆体。In the anti-collapse calcium-silicon-based composite bone cement material of the present invention, the solid-phase raw material is a calcium-silicon-based material with self-curing properties, and the liquid-phase raw material is a sodium alginate (SA) solution. Collapsible, injectable or moldable self-curing bone cement pastes.
本发明的抗溃散钙硅基复合骨水泥的制备方法具体包括以下步骤。The preparation method of the anti-collapse calcium-silicon-based composite bone cement of the present invention specifically includes the following steps.
(1)海藻酸钠溶液(1) Sodium alginate solution
分别称取不同质量的海藻酸钠(SA)粉体，加入去离子水中，于室温下搅拌1～5小时，得到不同浓度的海藻酸钠(SA)溶液。本发明中，海藻酸钠(SA)溶液的浓度可为0.1wt％～10wt％，优选为1wt％～2wt％。暂不使用时，可将海藻酸钠溶液于低温环境保存备用，例如置于4℃冰箱保存。Weigh sodium alginate (SA) powders of different masses, add them into deionized water, and stir at room temperature for 1-5 hours to obtain sodium alginate (SA) solutions with different concentrations. In the present invention, the concentration of the sodium alginate (SA) solution may be 0.1wt%-10wt%, preferably 1wt%-2wt%. When not in use, the sodium alginate solution can be stored in a low-temperature environment for future use, such as in a refrigerator at 4°C.
(2)钙硅基复合骨水泥的制备(2) Preparation of calcium-silica-based composite bone cement
将钙硅基骨水泥粉体与不同浓度的海藻酸钠(SA)溶液按照液固比为0.4～1.2mL/g的比例充分调和0.5～1分钟，得到具有抗溃散性质的钙硅基/海藻酸钠复合骨水泥浆体。当钙硅基骨水泥粉体与海藻酸钠(SA)溶液的液固比超出上述范围时，将会出现粉体不能固化或是固化时间过长等不利后果。所述钙硅基骨水泥粉体优选为具有自固化性能的钙硅基材料，更优选为硅酸三钙(Ca3SiO5，C3S)、硅酸二钙(Ca2SiO4，C2S)或硅酸三钙/硅酸二钙(Ca3SiO5/Ca2SiO4，C3S/C2S)混合粉体。硅酸三钙粉体的粒径范围可为1～100μm，硅酸二钙粉体粒径范围可为1～100μm。当选用硅酸三钙/硅酸二钙(Ca3SiO5/Ca2SiO4，C3S/C2S)混合粉体时，二者的质量比可为(0～100)：(100～0)，优选为(90～60)：(10～40)。Calcium-silica-based bone cement powder and different concentrations of sodium alginate (SA) solutions are fully reconciled at a liquid-solid ratio of 0.4-1.2mL/g for 0.5-1 minute to obtain calcium-silica-based/seaweed with anti-collapse properties Sodium Acid Composite Bone Cement Paste. When the liquid-solid ratio of the calcium-silica-based bone cement powder to the sodium alginate (SA) solution exceeds the above-mentioned range, there will be unfavorable consequences such as the powder cannot be solidified or the solidification time is too long. The calcium-silica-based bone cement powder is preferably a calcium-silica-based material with self-curing properties, more preferably tricalcium silicate (Ca3 SiO5 , C3 S), dicalcium silicate (Ca2 SiO4 , C2 S) or tricalcium silicate/dicalcium silicate (Ca3 SiO5 /Ca2 SiO4 , C3 S/C2 S) mixed powder. The particle size range of the tricalcium silicate powder can be 1-100 μm, and the particle size range of the dicalcium silicate powder can be 1-100 μm. When choosing tricalcium silicate/dicalcium silicate (Ca3 SiO5 /Ca2 SiO4 , C3 S/C2 S) mixed powder, the mass ratio of the two can be (0-100): (100 ~0), preferably (90~60): (10~40).
将上述骨水泥浆体于37℃，100％湿度的环境中养护。养护14天后，对骨水泥产物进行XRD及SEM分析，并作出性能评价。The above bone cement paste was maintained in an environment of 37° C. and 100% humidity. After curing for 14 days, XRD and SEM analysis were carried out on the bone cement product, and performance evaluation was made.
抗溃散性Collapse resistance
将不同浓度的海藻酸钠(SA)溶液分别以液固比0.4～1.2mL/g与钙硅基粉体混合、搅拌均匀后，将骨水泥浆体手动挤入去离子水中并观察浆体在水中的溃散情况：单纯钙硅基骨水泥在水中溃散迅速；含有海藻酸钠的复合骨水泥浆体在水中未有溃散现象发生。将上述复合骨水泥置于去离子水中并于120r/分钟条件震荡24小时后，复合骨水泥浆体的失重率小于5％，这说明该复合骨水泥具有优异的抗溃散性。Sodium alginate (SA) solutions of different concentrations were mixed with calcium-silicon-based powder at a liquid-solid ratio of 0.4-1.2 mL/g, and after stirring evenly, the bone cement slurry was manually squeezed into deionized water and observed. Collapse in water: Simple calcium-silica-based bone cement collapsed rapidly in water; composite bone cement paste containing sodium alginate did not collapse in water. After the composite bone cement was placed in deionized water and shaken at 120 r/min for 24 hours, the weight loss rate of the composite bone cement slurry was less than 5%, which indicated that the composite bone cement had excellent collapse resistance.
可注射性和可塑性injectability and plasticity
将不同浓度的海藻酸钠(SA)溶液分别以液固比0.4～1.2mL/g与钙硅基粉体混合、搅拌均匀，将骨水泥浆体置于注射器中静置5分钟，对其进行可注射性实验；将骨水泥浆体按压于模具的任意缺损部位，对其进行可塑性观察。本发明所述的复合骨水泥浆体静置5分钟后可注射率可达90％以上，这说明该复合骨水泥具有优异的可注射性，并且骨水泥浆体在按压过程中可根据缺损部位的形状任意塑形。Sodium alginate (SA) solutions of different concentrations were mixed with calcium-silicon-based powder at a liquid-solid ratio of 0.4-1.2 mL/g, and stirred evenly. The bone cement slurry was placed in a syringe and allowed to stand for 5 minutes. Injectability test: press the bone cement paste on any defect part of the mold, and observe its plasticity. The injectable rate of the composite bone cement paste of the present invention can reach more than 90% after standing for 5 minutes, which shows that the composite bone cement has excellent injectability, and the bone cement paste can be injected according to the defect site during the pressing process. The shape can be shaped arbitrarily.
固化时间和抗压强度Cure Time and Compressive Strength
将复合骨水泥浆体置于聚四氟乙烯模具(Ф6×12mm3)中，并置于37℃，100％湿度的环境中养护。用维卡仪分别测得几组浆体的初凝时间及终凝时间。该体系中，通过海藻酸钠(SA)含量的调控，复合骨水泥的初凝时间和终凝时间可分别在40～60分钟、60～160分钟内进行调控；养护28天后，抗压强度可达到20～60MPa。The composite bone cement paste was placed in a polytetrafluoroethylene mold (Ф6×12 mm3 ), and maintained in an environment of 37° C. and 100% humidity. The initial setting time and final setting time of several groups of slurries were measured with a Vicat instrument. In this system, by adjusting the content of sodium alginate (SA), the initial setting time and final setting time of the composite bone cement can be adjusted within 40-60 minutes and 60-160 minutes respectively; after 28 days of curing, the compressive strength can be Reach 20 ~ 60MPa.
矿化能力mineralization capacity
对钙硅基/海藻酸钠复合骨水泥采用模拟体液(SBF)中浸泡实验进行生物活性测试，并且对浸泡后的材料面进行SEM及EDS表征。本发明提供的钙硅基/海藻酸钠复合骨水泥能够诱导类骨磷灰石的生成，表明该材料具有良好的生物活性。The bioactivity of the calcium-silica-based/sodium alginate composite bone cement was tested by immersion in simulated body fluid (SBF), and the material surface after immersion was characterized by SEM and EDS. The calcium-silica-based/sodium alginate composite bone cement provided by the invention can induce the generation of bone-like apatite, indicating that the material has good biological activity.
降解性Degradability
对钙硅基/海藻酸钠复合骨水泥采用Tri-HCl浸泡实验进行体外降解测试。可通过调控海藻酸钠(SA)的含量对复合骨水泥的降解速率进行调控。The in vitro degradation test of calcium silicate/sodium alginate composite bone cement was carried out by Tri-HCl immersion test. The degradation rate of composite bone cement can be adjusted by adjusting the content of sodium alginate (SA).
细胞相容性Cytocompatibility
对养护3天后的钙硅基/海藻酸钠复合骨水泥的浸提液采用成骨细胞MC3T3进行体外细胞相容性实验。结果表明复合骨水泥材料浸提液的稀释液中，溶出的离子能明显刺激MC3T3的增殖。The in vitro cytocompatibility test was performed on the leaching solution of the calcium-silica-based/sodium alginate composite bone cement after 3 days of curing using osteoblast MC3T3. The results showed that the dissolved ions in the dilute solution of the extract of composite bone cement materials could significantly stimulate the proliferation of MC3T3.
本发明的有益效果：本发明的抗溃散钙硅基复合骨水泥材料具有良好的抗溃散性，其可注射性、可塑形性、凝固时间和力学强度等性能可以通过调节组成进行调控。此外，复合材料还具有良好的生物活性和可调控的降解性能，并且能够支持相关成骨细胞的增殖和分化。本发明具有制备工艺简单易行、成本低廉、易规模化制备等优点。Beneficial effects of the present invention: the anti-collapse calcium-silica-based composite bone cement material of the present invention has good collapse resistance, and its injectability, plasticity, setting time and mechanical strength can be regulated by adjusting the composition. In addition, the composite material also has good bioactivity and tunable degradation performance, and can support the proliferation and differentiation of related osteoblasts. The invention has the advantages of simple and easy preparation process, low cost, easy large-scale preparation and the like.
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。Examples are given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection. The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.
实施例1Example 1
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.2g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为1.0％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.2g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 1.0%, and store it in a 4°C refrigerator for later use;
2)硅酸三钙/海藻酸钠复合骨水泥的制备：2) Preparation of tricalcium silicate/sodium alginate composite bone cement:
将硅酸三钙粉体与1.0％海藻酸钠溶液以液固比0.6mL/g调和均匀，得到硅酸三钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为0.6％。于室温条件下测试该复合骨水泥浆体的抗溃散性、可注射性。结果表明，该复合骨水泥浆体在水中抗溃散效果明显(参见图3中的图b)；浆体在注射器中静置5分钟后可注射率接近100％(参见图4)，并且注射过程中没有固液分离现象，说明该复合骨水泥浆体适用于骨缺损的微创手术应用。图5示出钙硅基/海藻酸钠复合骨水泥的可塑性，由图5可看出该复合骨水泥具有优异的可塑性。将骨水泥浆体注模成型，于37℃，100％湿度条件下养护，并用维卡仪测定该复合骨水泥的初凝及终凝时间分别为57分钟和77分钟(参见图6)。图7示出该复合骨水泥的抗压强度，由图7可以看出养护28天后复合骨水泥的抗压强度可达55MPa。将该复合骨水泥片置于SBF中浸泡14天后，对骨水泥表面的沉积物进行SEM及EDS表征(参见图8)，结果表明表面沉积物为类骨磷灰石，这说明该复合骨水泥可诱导类骨磷灰石矿化。图9示出该复合骨水泥的降解性，由图9可以看出复合骨水泥的一个月后的降解后失重率可达55％。图10示出该复合骨水泥浸提液用于培养成骨细胞MC3T3的增殖结果，由图10可以看出该复合骨水泥具有良好的细胞相容性。Tricalcium silicate powder and 1.0% sodium alginate solution were uniformly mixed at a liquid-solid ratio of 0.6mL/g to obtain tricalcium silicate/sodium alginate composite bone cement slurry, and the content of sodium alginate was 0.6% at this time . The collapse resistance and injectability of the composite bone cement paste were tested at room temperature. The results show that the composite bone cement paste has obvious anti-collapse effect in water (see Figure b in Figure 3); the injectable rate of the slurry is close to 100% after standing in the syringe for 5 minutes (see Figure 4), and the injection process There is no solid-liquid separation in the results, indicating that the composite bone cement paste is suitable for minimally invasive surgery of bone defects. Fig. 5 shows the plasticity of the calcium silicate/sodium alginate composite bone cement, and it can be seen from Fig. 5 that the composite bone cement has excellent plasticity. The bone cement slurry was injection molded, maintained at 37°C and 100% humidity, and the initial setting and final setting times of the composite bone cement were measured by a Vicat instrument to be 57 minutes and 77 minutes respectively (see Figure 6). Figure 7 shows the compressive strength of the composite bone cement, and it can be seen from Figure 7 that the compressive strength of the composite bone cement can reach 55 MPa after 28 days of curing. After soaking the composite bone cement sheet in SBF for 14 days, the deposits on the surface of the bone cement were characterized by SEM and EDS (see Figure 8). The results showed that the surface deposits were bone-like apatite, which indicated that the composite bone cement Can induce bone-like apatite mineralization. Figure 9 shows the degradability of the composite bone cement, and it can be seen from Figure 9 that the weight loss rate of the composite bone cement after one month of degradation can reach 55%. FIG. 10 shows the proliferation result of the composite bone cement extract used to culture osteoblast MC3T3. It can be seen from FIG. 10 that the composite bone cement has good cytocompatibility.
实施例2Example 2
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.3g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为1.5％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.3g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 1.5%, and store it in a refrigerator at 4°C for later use;
2)硅酸三钙/海藻酸钠复合骨水泥的制备：2) Preparation of tricalcium silicate/sodium alginate composite bone cement:
将硅酸三钙粉体与1.5％海藻酸钠溶液以液固比0.6mL/g调和均匀，得到硅酸三钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为0.9％。于室温条件下测试该复合骨水泥浆体的抗溃散性、可注射性。结果表明，该复合骨水泥浆体在水中抗溃散效果明显(参见图3中的图c)；浆体在注射器中静置5分钟后可注射率接近100％(参见图4)，并且注射过程中没有固液分离现象，说明该复合骨水泥浆体适用于骨缺损的微创手术应用。将骨水泥浆体注模成型，于37℃，100％湿度条件下养护，并用维卡仪测定该复合骨水泥的初凝及终凝时间分别为60分钟和89分钟(参见图6)。图7示出该复合骨水泥的抗压强度，由图7可以看出养护28天后复合骨水泥的抗压强度可达27.9MPa，较硅酸三钙骨水泥来说，该复合骨水泥长期抗压强度略低。将该复合骨水泥片置于SBF中浸泡14天后，对骨水泥表面的沉积物进行SEM及EDS表征(参见图8)，结果表明表面沉积物为类骨磷灰石，这说明该复合骨水泥可诱导类骨磷灰石矿化。图9示出该复合骨水泥的降解性，由图9可以看出复合骨水泥的一个月后的降解后失重率可达58％，高于实例1中的复合骨水泥的降解后失重率。图10示出该复合骨水泥浸提液用于培养成骨细胞MC3T3的增殖结果，由图10可以看出该复合骨水泥具有良好的细胞相容性。Tricalcium silicate powder and 1.5% sodium alginate solution were evenly blended at a liquid-solid ratio of 0.6mL/g to obtain a tricalcium silicate/sodium alginate composite bone cement slurry. At this time, the content of sodium alginate was 0.9%. . The collapse resistance and injectability of the composite bone cement paste were tested at room temperature. The results show that the composite bone cement paste has obvious anti-collapse effect in water (see figure c in Figure 3); the injectable rate of the slurry is close to 100% after standing in the syringe for 5 minutes (see Figure 4), and the injection process There is no solid-liquid separation in the results, indicating that the composite bone cement paste is suitable for minimally invasive surgery of bone defects. The bone cement slurry was injection molded, maintained at 37°C and 100% humidity, and the initial setting and final setting times of the composite bone cement were measured by Vicat instrument as 60 minutes and 89 minutes respectively (see Figure 6). Figure 7 shows the compressive strength of the composite bone cement. It can be seen from Figure 7 that the compressive strength of the composite bone cement can reach 27.9MPa after 28 days of curing. The compressive strength is slightly lower. After soaking the composite bone cement sheet in SBF for 14 days, the deposits on the surface of the bone cement were characterized by SEM and EDS (see Figure 8). The results showed that the surface deposits were bone-like apatite, which indicated that the composite bone cement Can induce bone-like apatite mineralization. Figure 9 shows the degradability of the composite bone cement. It can be seen from Figure 9 that the weight loss rate of the composite bone cement after one month of degradation can reach 58%, which is higher than that of the composite bone cement in Example 1. FIG. 10 shows the proliferation result of the composite bone cement extract used to culture osteoblast MC3T3. It can be seen from FIG. 10 that the composite bone cement has good cytocompatibility.
实施例3Example 3
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.4g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为2.0％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.4g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 2.0%, and store it in a 4°C refrigerator for later use;
2)硅酸三钙/海藻酸钠复合骨水泥的制备：2) Preparation of tricalcium silicate/sodium alginate composite bone cement:
将硅酸三钙粉体与2.0％海藻酸钠溶液以液固比0.6mL/g调和均匀，得到硅酸三钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为1.2％。Tricalcium silicate powder and 2.0% sodium alginate solution were uniformly blended at a liquid-solid ratio of 0.6mL/g to obtain a tricalcium silicate/sodium alginate composite bone cement slurry. At this time, the content of sodium alginate was 1.2%. .
图1示出硅酸三钙以及上述实施例1～3制得的钙硅基/海藻酸钠复合骨水泥养护14天后的XRD图谱，由图1可以看出复合骨水泥的水化产物同硅酸三钙的水化产物没有明显区别。图2示出硅酸三钙以及上述实施例1～3制得的钙硅基/海藻酸钠复合骨水泥养护14天后的断面形貌，由图2可以看出海藻酸钠对复合骨水泥的断面形貌产生较大影响，其中，实施例1中(图2b所示)的断面结构更为致密。图3示出硅酸三钙以及上述实施例1～3制得的钙硅基/海藻酸钠复合骨水泥的抗溃散性，由图3可以看出本发明的复合骨水泥浆体在水中抗溃散效果明显。图4示出硅酸三钙以及上述实施例1～3制得的钙硅基/海藻酸钠复合骨水泥的可注射性，由图4可以看出相对于单纯的硅酸三钙骨水泥，该复合骨水泥的可注射率达90％以上，这说明该复合骨水泥具有优异的可注射性。Fig. 1 shows the XRD spectrum of tricalcium silicate and the calcium-silica-based/sodium alginate composite bone cement obtained in the above-mentioned Examples 1 to 3 after curing for 14 days. It can be seen from Fig. 1 that the hydration product of the composite bone cement is similar to that of silicon The hydration products of tricalcium acid were not significantly different. Fig. 2 shows the cross-sectional morphology of tricalcium silicate and the calcium-silica-based/sodium alginate composite bone cement obtained in the above-mentioned Examples 1 to 3 after 14 days of curing, and it can be seen from Fig. 2 that sodium alginate has an effect on the composite bone cement. The cross-sectional morphology has a greater impact, and the cross-sectional structure in Example 1 (shown in Figure 2b) is denser. Fig. 3 shows the anti-collapse property of tricalcium silicate and the calcium-silica base/sodium alginate composite bone cement that above-mentioned embodiment 1～3 makes, can find out that composite bone cement slurry of the present invention is resistant to water in water by Fig. 3 The collapse effect is obvious. Fig. 4 shows the injectability of tricalcium silicate and the calcium silicate-based/sodium alginate composite bone cement prepared in the above-mentioned Examples 1 to 3, as can be seen from Fig. 4 relative to simple tricalcium silicate bone cement, The injectability rate of the composite bone cement is over 90%, which shows that the composite bone cement has excellent injectability.
实施例4Example 4
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.3g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为1.5％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.3g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 1.5%, and store it in a refrigerator at 4°C for later use;
2)硅酸二钙/海藻酸钠复合骨水泥的制备：2) Preparation of dicalcium silicate/sodium alginate composite bone cement:
将硅酸二钙粉体与1.5％海藻酸钠溶液以液固比0.5mL/g调和均匀，得到硅酸二钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为0.75％。Dicalcium silicate powder and 1.5% sodium alginate solution were uniformly blended at a liquid-solid ratio of 0.5mL/g to obtain a dicalcium silicate/sodium alginate composite bone cement slurry. At this time, the content of sodium alginate was 0.75%. .
于室温条件下测试该复合骨水泥浆体的抗溃散性及可塑形性。结果表明，该复合骨水泥浆体在水中抗溃散效果明显；制作缺损骨模型，将复合骨水泥浆体按压入模型的缺损部位，骨水泥浆体在固化的过程中可以和缺损部位较好地贴合，说明该复合骨水泥浆体可以根据骨缺损的部位任意成型，适用于复杂形状骨缺损部位的填充。The collapse resistance and plasticity of the composite bone cement paste were tested at room temperature. The results show that the composite bone cement paste has obvious anti-collapse effect in water; the defect bone model is made, and the composite bone cement paste is pressed into the defect part of the model, and the bone cement paste can be well bonded to the defect part during the curing process. It fits well, indicating that the composite bone cement paste can be arbitrarily shaped according to the bone defect site, and is suitable for filling bone defect sites with complex shapes.
实施例5Example 5
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.4g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为2.0％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.4g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 2.0%, and store it in a 4°C refrigerator for later use;
2)硅酸三钙/硅酸二钙/海藻酸钠复合骨水泥的制备：2) Preparation of tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement:
将硅酸三钙粉体与硅酸二钙粉体按照4:1混合均匀后，与2.0％海藻酸钠溶液以液固比0.6mL/g调和均匀，得到硅酸三钙/硅酸二钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为1.2％。After mixing tricalcium silicate powder and dicalcium silicate powder uniformly at a ratio of 4:1, mix them with 2.0% sodium alginate solution at a liquid-solid ratio of 0.6mL/g to obtain tricalcium silicate/dicalcium silicate /Sodium alginate composite bone cement paste, the content of sodium alginate is 1.2%.
于室温条件下测试该复合骨水泥浆体的抗溃散性、可注射性。结果表明，该复合骨水泥浆体在水中抗溃散效果明显；浆体在注射器中静置5分钟后可注射率接近100％，并且注射过程中没有固液分离现象,说明该复合骨水泥浆体适用于骨缺损的微创手术应用。将复合骨水泥浆体注模成型，于37℃，100％湿度条件下养护后测试其抗压强度，复合骨水泥的抗压强度明显提升。The collapse resistance and injectability of the composite bone cement paste were tested at room temperature. The results show that the composite bone cement paste has obvious anti-collapse effect in water; the injectability rate of the paste is close to 100% after standing in the syringe for 5 minutes, and there is no solid-liquid separation phenomenon during the injection process, indicating that the composite bone cement paste Suitable for minimally invasive surgical applications in bone defects. The composite bone cement slurry was injection molded, and its compressive strength was tested after curing at 37°C and 100% humidity. The compressive strength of the composite bone cement was significantly improved.
实施例6Example 6
1)海藻酸钠溶液的配制：1) Preparation of sodium alginate solution:
称取0.4g海藻酸钠粉体溶解于20mL去离子水中，并于室温下搅拌均匀，最终得到浓度为2.0％海藻酸钠溶液，置于4℃冰箱保存，备用；Weigh 0.4g of sodium alginate powder and dissolve it in 20mL of deionized water, and stir evenly at room temperature to finally obtain a sodium alginate solution with a concentration of 2.0%, and store it in a 4°C refrigerator for later use;
2)硅酸三钙/硅酸二钙/海藻酸钠复合骨水泥的制备：2) Preparation of tricalcium silicate/dicalcium silicate/sodium alginate composite bone cement:
将硅酸三钙粉体与硅酸二钙粉体按照4:1混合均匀后，与2.0％海藻酸钠溶液以液固比0.5mL/g调和均匀，得到硅酸三钙/硅酸二钙/海藻酸钠复合骨水泥浆体，此时海藻酸钠的含量为1.0％。After mixing tricalcium silicate powder and dicalcium silicate powder uniformly at a ratio of 4:1, mix them with 2.0% sodium alginate solution at a liquid-solid ratio of 0.5mL/g to obtain tricalcium silicate/dicalcium silicate /Sodium alginate composite bone cement paste, the content of sodium alginate is 1.0%.
于室温条件下测试该复合骨水泥浆体的抗溃散性及可塑形性。结果表明，该复合骨水泥浆体在水中抗溃散效果明显，并且复合骨水泥浆体在固化过程中可以和复杂形状缺损贴合，说明该复合骨水泥浆体可以根据骨缺损的部位任意成型，适用于复杂形状骨缺损部位的填充。The collapse resistance and plasticity of the composite bone cement paste were tested at room temperature. The results show that the composite bone cement paste has obvious anti-collapse effect in water, and the composite bone cement paste can be fitted with complex-shaped defects during the curing process, which shows that the composite bone cement paste can be arbitrarily shaped according to the position of the bone defect, It is suitable for filling bone defects with complex shapes.
产业应用性：本发明的抗溃散钙硅基复合骨水泥材料具有优异的可注射性、可塑性及抗溃散性，可用于微创治疗或复杂骨缺损形状的填充。Industrial Applicability: The anti-collapse calcium-silica-based composite bone cement material of the present invention has excellent injectability, plasticity and anti-collapse property, and can be used for minimally invasive treatment or filling of complex bone defect shapes.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510797255.XACN106693063B (en) | 2015-11-18 | 2015-11-18 | A kind of anti-collapse calcium-silica-based composite bone cement and its preparation method and application |
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| CN201510797255.XACN106693063B (en) | 2015-11-18 | 2015-11-18 | A kind of anti-collapse calcium-silica-based composite bone cement and its preparation method and application |
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| CN201510797255.XAActiveCN106693063B (en) | 2015-11-18 | 2015-11-18 | A kind of anti-collapse calcium-silica-based composite bone cement and its preparation method and application |
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