CN1292804C - Preparation process of strontium nano calcium phosphate containing biological active bone cement - Google Patents

Preparation process of strontium nano calcium phosphate containing biological active bone cement Download PDF

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CN1292804C
CN1292804C CN 200410025920 CN200410025920A CN1292804C CN 1292804 C CN1292804 C CN 1292804C CN 200410025920 CN200410025920 CN 200410025920 CN 200410025920 A CN200410025920 A CN 200410025920A CN 1292804 C CN1292804 C CN 1292804C
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strontium
cement
bone
calcium phosphate
powder
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CN1559888A (en )
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郭大刚
徐可为
憨勇
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西安交通大学
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Abstract

本发明公开了一种缓释特殊药理性锶元素且无毒副作用的含锶纳米磷酸钙生物活性骨水泥的制备工艺。 The present invention discloses a sustained release of strontium particular pharmacological and toxic side effects of the preparation of strontium-containing calcium phosphate nano bioactive bone cement. 本制备工艺采取水泥固相为一定颗粒度分布且按一定摩尔比配制的Ca This preparation process must take cement solid phase and the particle size distribution of the ratio must be formulated Ca

Description

含锶纳米磷酸钙生物活性骨水泥的制备工艺 Preparation process of calcium phosphate nano-strontium-containing bioactive cement

技术领域 FIELD

本发明涉及含锶纳米磷酸钙生物活性水泥的制备技术,尤其涉及一种缓释特殊药理性锶元素且无毒副作用的含锶羟基磷灰石骨修复材料的制备工艺。 The present invention relates to a nano-technology strontium phosphate bioactive cement, more particularly to a sustained release of strontium particular pharmacological and toxic side effects of the preparation of strontium-containing hydroxyapatite bone repair materials.

背景技术 Background technique

磷酸钙骨水泥(Calcium Phosphate Cement,简称CPC),属多孔结构且固化产物是羟基磷灰石,具有良好的生物相容性、骨传导性,尤其可处理成浆料形式直接注入骨缺陷中并原位固化,因而在牙科骨替代、矫正及重建外科中得到广泛应用。 Calcium phosphate cement (Calcium Phosphate Cement, referred to as CPC), a porous metal structure and the cured product is hydroxyapatite, have good biocompatibility, osteoconductivity, in particular, can be processed into a slurry form and directly injected into a bone defect cured in situ, and thus bone replacement, correction and reconstruction surgery is widely used in dentistry. 磷酸钙骨水泥主要由两部分组成:磷酸钙粉末与固化液。 Calcium phosphate cement is mainly composed of two parts: calcium phosphate powder with a curing liquid. 固化液一般是水或者稀磷酸水溶液,磷酸钙粉末主要有磷酸四钙(Ca4(PO4)2O)、磷酸氢钙(CaHPO4·2H2O或CaHPO4)、磷酸二氢钙(Ca(H2PO4)2·H2O或Ca(H2PO4)2)、磷酸八钙(Ca8H2(PO4)2·5H2O)、磷酸三钙(α-或β-Ca3(PO4)2)、焦磷酸钙(Ca2P2O7)等。 Curing liquid is generally water or a dilute aqueous solution of phosphoric acid, calcium phosphate powder mainly tetracalcium phosphate (Ca4 (PO4) 2O), dicalcium phosphate (CaHPO4 · 2H2O or CaHPO4), monocalcium phosphate (Ca (H2PO4) 2 · H2O or Ca (H2PO4) 2), octacalcium phosphate (Ca8H2 (PO4) 2 · 5H2O), tricalcium phosphate (alpha] or β-Ca3 (PO4) 2), calcium pyrophosphate (Ca2P2O7) and the like. 此外,据报道,锶(Sr)是人体中存在的一种微量元素,在骨中的含量约占其重量的0.01%,人体中含有的99%以上的Sr、Ca均积聚在骨骼之中。 Further, it is reported, strontium (Sr) is a trace element present in the human body, the content of which in the bone about 0.01% by weight, the body contains 99% or more of Sr, Ca are accumulated in the bones. Sr与Ca均属碱土金属,具有许多相似的性质。 It belongs to the alkaline earth metal Ca and Sr, having a number of similar properties. 以离子形态存在的Sr2+分享着与Ca2+相同的生理路线,最终沉积在骨的矿化结构中(Blake,GM et al..Sr-89 therapystrontium kineticls in metastatic bone disease.J.Nucl.Med.1986,27:1030/Blake,DM,et al.Sr-89 strontium kineticls in disseminated carcinoma of the prostate.Eur.J.Nucl.Med.1986,12:447-454)。 Ions present in the form of Sr2 + and Ca2 + share the same physical route, in the final deposition of mineralized bone structure (Blake, GM et al..Sr-89 therapystrontium kineticls in metastatic bone disease.J.Nucl.Med.1986, 27: 1030 / Blake, DM, et al.Sr-89 strontium kineticls in disseminated carcinoma of the prostate.Eur.J.Nucl.Med.1986,12: 447-454). 已有研究表明,锶具有以下几个方面的特殊药理作用:首先,在骨骼病区的矿化与重建方面,低剂量的锶有助于增加骨的质量与体积,目前尚未没有发现它对矿化形貌和矿物化学组成产生不利的影响(Grynpa MD,et al.Strontium increases vertebral bone volume in rats at a low dosethat does not induce detectable mineralizaion defect.Bone,1996,18:253~259);其次,在骨代谢方面,在外界不断供给条件下,锶在骨中的含量因体内解剖学位置不同而异,并发现锶可以与骨中磷灰石晶体表面的少量钙发生交换(Dahl,SG,Allain,P.,Marie,PL,et al.Incorporation and Distribution of Strontium in Bone.Bone.2001,28(4):446-453);其三,在骨传导性方面,Johal等比较了不同含锶量的玻璃离子水泥后,发现含锶量最高组LG125具有最好的骨传导性(Johal KK,etal.In vivo response of strontium and zince-based ionomeric cement implants in bone.Jou Studies have shown that strontium has a special pharmacological action following aspects: First, in the reconstruction of bone mineralization and ward aspect, low doses of strontium helps to increase bone mass and volume, it has not yet found no mine the morphology and chemical composition of the mineral adversely affect (Grynpa MD, et al.Strontium increases vertebral bone volume in rats at a low dosethat does not induce detectable mineralizaion defect.Bone, 1996,18: 253 ~ 259); secondly, the bone metabolism, in the constant supply of external conditions, the content of strontium in the bone due to different anatomical location-vivo, and found that the strontium exchange may occur (Dahl, SG, Allain with a small amount of bone calcium apatite crystal surface, P., Marie, PL, et al.Incorporation and Distribution of strontium in Bone.Bone.2001,28 (4): 446-453); Third, in terms of osteoconductive, like Comparative Johal strontium containing different amounts of after the glass ionomer cement, with the highest amount of strontium was found to have the best group LG125 osteoconductive (Johal KK, etal.In vivo response of strontium and zince-based ionomeric cement implants in bone.Jou rnal of materials science:materials in medicine.2002,13:375-379);其四,在治疗骨质疏松病症方面,锶也发挥了显著疗效,近年来,发现Strontium ranelate(S12911)是一种很有应用潜力的抗骨质疏松药物,体内外实验均表明,S12911具有刺激骨的形成、抑制骨再吸收的作用(Canalis,E.,Hott,M.,Deloffre,P.,Tsouderos,Y.,and Marie,PJThe divalent strontium salt S12911 enhances bonecell replication and bone formation in vitro.Bone 1996,8:517-523);其五,早在1988年,89SrCl2就被批准为一种减轻病人痛苦的镇静剂,往往在其它治疗方法无效时,它却发挥显著疗效(Lewington,VJ,Zivanovic,MA,Blake,GB,et al.Treatment ofbone pain indisseminated prostrate cancer using strontium-89.Nucl.Med.Commun.1988,9:172-186)。 rnal of materials science: materials in medicine.2002,13: 375-379); Fourth, a disorder in the treatment of osteoporosis, strontium also play a significant effect, in recent years, found Strontium ranelate (S12911) is a useful anti-osteoporosis drugs of potential applications, in vivo experiments show that, S12911 having a stimulating bone formation and inhibiting bone resorption effect (Canalis, E., Hott, M., Deloffre, P., Tsouderos, Y., and Marie, PJThe divalent strontium salt S12911 enhances bonecell replication and bone formation in vitro.Bone 1996,8: 517-523); Fifth, as early as 1988, 89SrCl2 was approved as a sedative to alleviate the suffering of patients, often in other the method of treatment fails, it plays a significant effect (Lewington, VJ, Zivanovic, MA, Blake, GB, et al.Treatment ofbone pain indisseminated prostrate cancer using strontium-89.Nucl.Med.Commun.1988,9: 172-186 ). 此外,国内外学者还研究表明,低剂量Sr(一般低于10%)置换磷灰石中部分钙而获得的含锶羟基磷灰石,不仅具有较之纯羟基磷灰石更好的组织相容性、骨传导性、甚至一定程度上的骨诱导能力(廖大鹏,周正炎,顾云峰等.锶磷灰石修复下颌骨缺损的实验研究.上海口腔医学.2000;9(2):73~75),还改变了其溶解动力学,提高了生物降解性(J.Christoffersen,MRChristoffersen,N.Kolthoff,et al.Effects of strontium ions on growth and dissolutionof hydroxtapatite and on bone mineral detection.Bone.1997,20(1):47~54)。 In addition, further studies have shown that scholars, strontium hydroxyapatite low dose Sr (generally less than 10%) replacement of part of the calcium apatite obtained, not only pure hydroxyapatite better than the tissues capacitive, osteoconductive, osteoinductive capability even experimental study (Liaoda Peng, Zhou Yan, Gu Yunfeng like strontium apatite certain degree of mandibular defects Shanghai Journal of Stomatology. 2000; 9 (2): 73-75 ), which also changes the dissolution kinetics, improve the biodegradability (J.Christoffersen, MRChristoffersen, N.Kolthoff, et al.Effects of strontium ions on growth and dissolutionof hydroxtapatite and on bone mineral detection.Bone.1997,20 ( 1): 47 to 54). 因此,若将锶掺入磷酸钙骨水泥中,获得含锶磷灰石产物,既可保持传统骨水泥的诸多优点,又可充分发挥锶或者含锶磷灰石的上述良好药理性能或者生物学性能。 Thus, when incorporating strontium calcium phosphate cement, the product was obtained containing strontium apatite, bone cement can maintain the traditional advantages, but also full or strontium-containing biological or pharmacological properties well above strontium apatite performance. 2001年法国学者(L.Lerous,JLLacout.Preparation of calcium strontiumhydroxyapatites by a new route involving calcium phosphate cements.J.Mater.Res.2001,16(1):171~178)首次采用制备磷酸钙骨水泥的方法合成了含锶羟基磷灰石,采用的固相粉末为Ca4(PO4)2O和α-Ca3(PO4)2,液相为Sr(NO3)2与H3PO4的水溶液,但缺点是最终固化产物中含有大量对人体组织不利的NO3-离子,不适于临床上人体骨修复等应用,有关力学性能方面的后续研究及类似内容还未见报道。 In 2001 French scholar (L.Lerous, JLLacout.Preparation of calcium strontiumhydroxyapatites by a new route involving calcium phosphate cements.J.Mater.Res.2001,16 (1): 171 ~ 178) for the first time a method for preparing calcium phosphate cement synthesis of strontium-containing hydroxyapatite powder used as a solid phase Ca4 (PO4) 2O, and α-Ca3 (PO4) 2, the liquid phase is an aqueous solution of Sr (NO3) 2 and H3PO4, but the drawback is that the final product contains a cured a large number of human tissue adverse NO3- ion, follow-up research applications related to the mechanical properties of human bone repair and other aspects of clinical unsuitable and the like have not been reported.

发明内容 SUMMARY

本发明的目的在于提供一种具有缓释特殊药理性锶离子且无毒副作用的含锶纳米磷酸钙生物活性骨水泥的制备工艺。 Object of the present invention to provide a sustained release preparation having a specific pharmacological and toxic side effects of strontium ion containing strontium phosphate nano bioactive bone cement.

本发明的技术方案是这样解决的:1)固相粉末的组成:将Ca4(PO4)2O、SrHPO4、CaHPO4粉末按照摩尔比2∶x∶(2-x)混和,其中x=0.1~1;2)液相的制备:配制浓度为0.5~1mol/l的磷酸H3PO4水溶液作为水泥固化液。 Aspect of the present invention is solved by: 1) the solid phase composition of the powder: the Ca4 (PO4) 2O, SrHPO4, CaHPO4 powder molar ratio 2:x: (2-x) mixture, where x = 0.1 ~ 1; preparation of the liquid phase 2): preparing an aqueous solution of a concentration of phosphoric acid H3PO4 0.5 ~ 1mol / l solution of a cementation.

3)固/液比选择:固相粉末与液相调和时的质量比为1.5~3.0。 3) Solid / liquid ratio selection: mass ratio of the solid powder and liquid blending 1.5 to 3.0.

采用本发明的制备工艺制成的含锶纳米磷酸钙生物活性骨水泥,其最终固化产物为掺锶缺钙羟基磷灰石(Ca(10-x)Srx(PO4)(6+1.005z/y+0.047xz)2OH),钙磷摩尔比Ca/P为1.48~1.62,微观形态为菊花瓣(瓣厚40~45nm,宽300~350nm)或曲棒状(直径40~50nm,长1.0~1.5μm)纳米晶体结构。 It prepared using the process of the present invention is made of strontium-containing nano-calcium phosphate bioactive cement, which is the final cured product of strontium deficient hydroxyapatite (Ca (10-x) Srx (PO4) (6 + 1.005z / y + 0.047xz) 2OH), calcium and phosphorus molar ratio of Ca / P of 1.48 to 1.62, the morphology of petal (flap thickness 40 ~ 45nm, width of 300 ~ 350nm) or curved rod-shaped (diameter of 40 ~ 50nm, length of 1.0 ~ 1.5μm ) nanocrystal structure.

采用本发明的制备工艺制成的含锶纳米磷酸钙生物活性骨水泥,其固化后的压缩强度为40~60MPa,初凝时间为4~11min,终凝时间为10~17min,适合人体非负载部位的骨修复。 Prepared using the process of the invention made of non-supported body containing strontium phosphate nano bioactive bone cement, the compressive strength after curing of 40 ~ 60MPa, initial setting time is 4 ~ 11min, final setting time of 10 ~ 17min, for bone repair site. 固相粉末磷酸四钙Ca4(PO4)2O、磷酸氢锶SrHPO4、磷酸氢钙CaHPO4的平均粒度范围分别为8~13μm、0.7~1.3μm、0.8~1.5μm。 Solid powder tetracalcium phosphate Ca4 (PO4) 2O, strontium hydrogen phosphate SrHPO4, calcium hydrogen phosphate CaHPO4 average particle size range of 8 ~ 13μm, respectively, 0.7 ~ 1.3μm, 0.8 ~ 1.5μm.

采用本发明的制备工艺制成的含锶纳米磷酸钙生物活性骨水泥,具有缓释锶离子作用,从而延长锶离子对植入部位的药理性治疗功效,而且锶与部分钙的置换有利于提高这种骨水泥的降解性。 The present invention is made of nano-preparation containing strontium phosphate bioactive bone cement, having a sustained release effect of strontium ions, strontium ions thereby extending the pharmacological efficacy of the treatment site of implantation, calcium and strontium partial replacement help improve this degradation of the bone cement.

具体实施方式 detailed description

下面结合实施例对本发明的内容作进一步详细说明:实施例1:将0.6g水泥混合粉末与0.4g浓度为1mol/l的H3PO4水溶液(其中x=0.5,即Sr/(Sr+Ca)=5%;固/液质量比为1.5∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF(模拟体液)中,每隔3天更换一次SBF,2周后形成固化体的最终产物成分为含锶缺钙羟基磷灰石(Ca9.5Sr0.5(PO4)6.692OH,Ca/P=1.49)。 Below in connection with embodiments of the present invention will be further described in detail: Example 1: The cement powder is mixed with 0.6g 0.4g H3PO4 aqueous solution at a concentration of 1mol / l (where x = 0.5, i.e. Sr / (Sr + Ca) = 5 %; solid / liquid mass ratio of 1.5) 30s with a spatula to form a uniform blending of the cement slurry filled diameter 6mm, 12mm high stainless steel cylindrical mold and applying a compaction pressure of 0.7MPa, the after the sample was made into a cylinder diameter of 6.5mm, 13mm high glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for the curing, curing 15min, the sample was quickly removed and immersed in SBF (SBF) in the SBF replaced once every three days, two weeks after the final formed product is cured composition containing strontium deficient hydroxyapatite (Ca9.5Sr0.5 (PO4) 6.692OH, Ca / P = 1.49 ). 试样在SBF中浸泡1天的平均压缩强度为53.16MPa,最大压缩强度为60.20MPa。 Sample 1 day immersion in SBF average compression strength of 53.16MPa, maximum compressive strength of 60.20MPa. 2周后的平均压缩强度为47.37MPa,最大压缩强度为51.72MPa。 The average compressive strength after 2 weeks of 47.37MPa, maximum compressive strength of 51.72MPa. 初凝时间为5.5min,终凝时间为12min。 Initial setting time 5.5min, final setting time was 12min. 细胞毒性试验结果为0级。 Cytotoxicity test result is 0. 在生理盐水中静态浸泡实验结果表明,随浸泡时间延长,锶的释放量逐渐增加但较缓慢,4周后锶释放量为其总量的7.4%。 In physiological saline static soak results show that, with the immersion time, but increasing strontium slow release, strontium 7.4% of its total release after 4 weeks.

实施例2:将0.6g水泥混合粉末与0.24g浓度为0.5mol/l的H3PO4水溶液(其中x=0.5,即Sr/(Sr+Ca)=5%;固/液质量比为2.5∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成分为含锶缺钙羟基磷灰石(Ca9.5Sr0.5(PO4)6.212OH,Ca/P=1.61)。 Example 2: 0.6g of cement powder is mixed with an aqueous solution of H3PO4 0.24g concentration 0.5mol / l (where x = 0.5, i.e. Sr / (Sr + Ca) = 5%; solid / liquid mass ratio is 2.5) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post-curing 15min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium deficient hydroxyapatite (Ca9.5Sr0.5 (PO4) 6.212OH, Ca / P = 1.61). 试样在SBF中浸泡1天的平均压缩强度为51.55MPa,最大压缩强度为57.68MPa。 Sample 1 day immersion in SBF average compression strength of 51.55MPa, maximum compressive strength of 57.68MPa. 初始凝结时间为4min,最终凝结时间为10min。 The initial setting time was 4min, the final setting time was 10min.

实施例3:将0.6g水泥混合粉末与0.3g浓度为0.5mol/l的H3PO4水溶液(其中x=0.5,即Sr/(Sr+Ca)=5%;固/液质量比为2.0∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成分为含锶缺钙羟基磷灰石(Ca9.5Sr0.5(PO4)6.262OH,Ca/P=1.60)。 Example 3: The cement powder is mixed with 0.6g 0.3g H3PO4 aqueous solution at a concentration of 0.5mol / l (where x = 0.5, i.e. Sr / (Sr + Ca) = 5%; solid / liquid mass ratio 2.0:1) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post-curing 15min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium deficient hydroxyapatite (Ca9.5Sr0.5 (PO4) 6.262OH, Ca / P = 1.60). 试样在SBF中浸泡1天的平均压缩强度为45.12MPa,最大压缩强度为47.77MPa。 Sample 1 day immersion in SBF average compression strength of 45.12MPa, maximum compressive strength of 47.77MPa. 初始凝结时间为7min,最终凝结时间为13min。 The initial setting time is 7min, the final setting time was 13min.

实施例4,将0.6g水泥混合粉末与0.4g浓度为1.0mol/l的H3PO4水溶液(其中x=1,即Sr/(Sr+Ca)=10%;固/液质量比为1.5∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成分为含含锶缺钙羟基磷灰石(Ca9Sr(PO4)6.722OH,Ca/P=1.49)。 Example 4, the cement powder is mixed with 0.6g 0.4g H3PO4 aqueous solution at a concentration of 1.0mol / l (where x = 1, i.e. Sr / (Sr + Ca) = 10%; solid / liquid mass ratio is 1.5) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post-curing 15min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium-containing calcium hydroxyapatite (Ca9Sr (PO4) 6.722OH, Ca / P = 1.49). 试样在SBF中浸泡1天的平均压缩强度为36.92MPa,最大压缩强度为45.01MPa。 Sample 1 day immersion in SBF average compression strength of 36.92MPa, maximum compressive strength of 45.01MPa. 初始凝结时间为6min,最终凝结时间为13min。 The initial setting time was 6min, the final setting time was 13min. 细胞毒性试验结果为0级。 Cytotoxicity test result is 0. 在生理盐水中静态浸泡实验结果表明,4周后锶释放量为其总量的14.16%。 In physiological saline static soak results show that, after 4 weeks 14.16% for the total release of strontium.

实施例5:将0.6g水泥混合粉末与0.24g浓度为0.5mol/l的H3PO4水溶液(其中x=1,即Sr/(Sr+Ca)=10%;固/液质量比为2.5∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化20min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成份为含含锶缺钙羟基磷灰石(Ca9Sr(PO4)6.222OH,Ca/P=1.61)。 Example 5: 0.6g 0.24g cement powder is mixed with an aqueous solution of H3PO4 concentration of 0.5mol / l (where x = 1, i.e. Sr / (Sr + Ca) = 10%; solid / liquid mass ratio is 2.5) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post curing 20min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium-containing calcium hydroxyapatite (Ca9Sr (PO4) 6.222OH, Ca / P = 1.61). 试样在SBF中浸泡1天的平均压缩强度为44.41MPa,最大压缩强度为47.77MPa。 Sample 1 day immersion in SBF average compression strength of 44.41MPa, maximum compressive strength of 47.77MPa. 初始凝结时间为11min,最终凝结时间为17min。 The initial setting time was 11min, the final setting time was 17min.

实施例6:将0.6g水泥混合粉末与0.20g浓度为0.5mol/l的H3PO4水溶液(其中x=1,即Sr/(Sr+Ca)=10%;固/液质量比为3.0∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成份为含锶缺钙羟基磷灰石(Ca9Sr(PO4)6.192OH,Ca/P=1.62)。 Example 6: 0.6g 0.20g cement powder is mixed with an aqueous solution of H3PO4 concentration of 0.5mol / l (where x = 1, i.e. Sr / (Sr + Ca) = 10%; solid / liquid mass ratio 3.0:1) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post-curing 15min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium deficient hydroxyapatite (Ca9Sr (PO4) 6.192OH, Ca / P = 1.62). 试样在SBF中浸泡1天的平均压缩强度为44.32MPa,最大压缩强度为47.77MPa。 Sample 1 day immersion in SBF average compression strength of 44.32MPa, maximum compressive strength of 47.77MPa. 初始凝结时间为7.5min,最终凝结时间为14min。 The initial setting time was 7.5min, final setting time was 14min.

实施例7:将0.6g水泥混合粉末与0.40g浓度为0.5mol/l的H3PO4水溶液(其中x=0.1,即Sr/(Sr+Ca)=1%;固/液质量比为1.5∶1)用药匙调和30s以形成均匀一致的水泥浆料,填入直径为6mm、高为12mm的不锈钢圆柱体模具中并施加0.7MPa的压力压实,将制成的圆柱体试样塞进直径6.5mm、高13mm的玻璃管中,然后置入温度为37℃、相对湿度为100%的环境中固化,固化15min后,将试样取出并迅速浸入SBF中,每隔3天更换一次SBF,2周后形成固化体的最终产物成份为含锶缺钙羟基磷灰石(Ca9.9Sr0.1(PO4)6.342OH,Ca/P=1.58)。 Example 7: 0.6g 0.40g cement powder is mixed with an aqueous solution of H3PO4 concentration of 0.5mol / l (where x = 0.1, i.e. Sr / (Sr + Ca) = 1%; solid / liquid mass ratio is 1.5) Harmonic 30s with a spatula to form a cement slurry uniform, fill diameter 6mm, 12mm high stainless steel cylindrical mold and applying a pressure of 0.7MPa compaction, the sample was made into a cylinder diameter of 6.5mm high 13mm glass tube, then placed in a temperature of 37 ℃, relative humidity of 100% for curing, post-curing 15min, the sample was quickly removed and immersed in the SBF, SBF replaced once every three days, 2 circumferential the final product composition is cured after the formation of strontium deficient hydroxyapatite (Ca9.9Sr0.1 (PO4) 6.342OH, Ca / P = 1.58). 试样在SBF中浸泡1天的平均压缩强度为50.15MPa,最大压缩强度为56.37MPa。 Sample 1 day immersion in SBF average compression strength of 50.15MPa, maximum compressive strength of 56.37MPa. 初始凝结时间为5.0min,最终凝结时间为11min。 The initial setting time was 5.0min, final setting time was 11min.

Claims (1)

  1. 1.含锶纳米磷酸钙生物活性骨水泥的制备工艺,其特征在于:1)固相粉末组成:将磷酸四钙Ca4(PO4)2O、磷酸氢锶SrHPO4、磷酸氢钙CaHPO4粉末按照摩尔比2∶x∶(2-x)混和,其中x=0.1~1;2)液相的制备:配制浓度为0.5~1mol/l的磷酸H3PO4水溶液作为固化液;3)固/液比选择:将固相粉末与液相进行调和,调和时固相粉末与液相质量比为1.5~3.0∶1。 1. Preparation of strontium containing calcium phosphate nanometer bioactive bone cement, characterized in that: 1) a solid phase powder composed of: 2O, strontium hydrogen phosphate SrHPO4, calcium hydrogen phosphate CaHPO4 powder in a molar ratio tetracalcium phosphate Ca4 (PO4) 2 :x: (2-x) mixture, where x = 0.1 ~ 1; preparation of liquid phase 2): preparing an aqueous solution of a concentration of phosphoric acid H3PO4 0.5 ~ 1mol / l as the curing fluid; 3) the solid / liquid ratio selection: the solid blending with powder and liquid phase, a solid phase and a liquid phase powder mass ratio of 1.5 to 3.0:1 harmonic.
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US6459010B1 (en) * 1997-12-23 2002-10-01 Commissariat A L'energie Atomique Method for packaging industrial, in particular radioactive, waste in apatite ceramics
CN1377711A (en) * 2002-04-17 2002-11-06 西安交通大学 Method for preparing degradable biologically active artificial bone

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