CN105712737A - 一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法 - Google Patents
一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,属于生物医用材料制备技术领域。将锶掺杂羟基磷灰石粉末(50%~80%)与碳酸氢铵造孔剂粉末(50%~20%)按质量比称取后进行进行混料,混合均匀后经机械压制成块体压坯,再将压坯放入石墨模具,置入放电等离子烧结炉进行烧结,随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。利用本发明制备骨修复用多孔锶掺杂羟基磷灰石材料无需添加任何粘结剂和模板剂,成分纯净无有害杂质,孔隙率在20~40%之间可控,降解速率适宜,具有良好的成骨诱导能力,并且工艺简单易行、快速高效、成本低廉且易于实现工业化生产,可以用于机体硬组织再生或重建的骨缺损修复材料。
Description
技术领域
本发明涉及一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,属于生物医用材料制备技术领域。
背景技术
近年来,随着国民经济的快速发展以及各类工伤和交通事故的频繁发生,在临床医疗过程中经常遇到重建或再生因病或由于外伤造成的骨缺损情况,需要大量的骨缺损修复材料。目前临床应用最为广泛的骨缺损修复材料是自体骨和同种异体骨,但是存在来源不足、供骨区并发症、移植排异反应、疾病传播及融合时间较长等问题,限制了其应用,因而需要研究和开发新型人造骨修复材料以满足临床上的大量需求。
目前研究最多的骨修复材料是羟基磷灰石(Hydroxyapatite,Ca10(PO4)6(OH)2,简称HA)。互连多孔的HA骨修复材料不仅具有与骨组织的生长速度较匹配的降解速率,而且还能满足骨组织及血管长入的要求,加快骨缺损修复的过程。植入体内后,能与骨组织通过化学键合形成紧密结合、有良好的骨传导作用,对新骨的生长具有一定的诱导作用,不致溶血或凝血、无全身或局部毒性反应、不致突变等不良反应;并且还具有良好的生物可降解性,当其植入体内后会逐步降解,降解后的Ca、P进入体内循环系统构成新生骨或者随新陈代谢排出体外,一定时间后材料完全降解,并被新生骨取代。因此,多孔HA骨修复材料成为一种非常理想的、临床应用前景非常广阔的机体硬组织再生或重建的骨缺损修复材料之一。
国内外目前制备多孔HA基骨修复材料的方法主要有化学发泡法(H2O2、碳酸盐、亚硫酸盐等作为发泡剂,聚乙烯醇作为粘结剂)、聚合物泡沫模板浸渍法(聚氨酯海绵作为造孔材料,聚乙烯醇或硅酸钠作为粘结剂)、凝胶注模成型法(蜡球作造孔剂,聚乙烯醇作为粘结剂)、造孔剂法(碳酸氢铵、萘、氢化钛及乙基纤维素作造孔剂,聚乙烯醇作为粘结剂)等。但是上述方法存在以下问题:(1)为了提高材料的力学性能和获得稳定的多孔结构,上述方法制备过程中往往需要对材料进行较长时间的高温烧结过程。而过高的烧结温度和较长的保温时间会造成HA发生部分分解,由于HA的分解产物与HA的降解速率不一致,导致材料的降解速率与骨组织爬行替代速率不匹配,使得材料的骨缺损修复能力降低;(2)上述方法制备材料的过程中需要加入粘结剂(如聚乙烯醇、硅酸钠等),尽管在高温烧结过程中粘结剂绝大部分会分解挥发,但仍然有少量的粘结剂残留在材料中。这些残留的粘结剂如硅酸钠不会降解,会影响微血管及骨组织的长入,降低材料的生物相容性和成骨活性,而聚乙烯醇已被证明具有肝和胆囊组织毒性;(3)上述方法在制备多孔HA材料的过程中容易引入杂质,会对材料的生物相容性造成不利影响。因而利用上述方法制备的多孔HA骨修复材料不能完全满足临床使用的要求,需要寻找新的制备方法来克服上述制备方法存在的问题。
多孔HA基骨修复材料除了在制备技术上存在诸多的不足之外,在临床实验中还发现,尽管其具有一定的成骨诱导活性,但是促进成骨和抑制破骨的能力还有待提高。与自体骨和同种异体骨相比,新骨生长时间仍然较长,延长了骨缺损修复的过程。需要进一步提高骨修复材料的成骨诱导能力,减少病人的痛苦,以提高骨缺损修复的治疗效果。
发明内容
本发明的目的在于针对现有技术和材料的不足,提供一种利用放电等离子烧结制备骨修复用多孔锶掺杂羟基磷灰石材料的方法,获得成分纯净无有害杂质、孔隙率可控、降解速率适宜、具有良好成骨诱导能力的骨修复用多孔锶掺杂羟基磷灰石材料,满足临床上对用于机体硬组织再生或重建的骨缺损修复材料的性能要求,推进其临床应用。
本发明的技术方案是:一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,经过下列工艺步骤:
(1)按锶掺杂羟基磷灰石50%~80%、碳酸氢铵50%~20%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末;
(2)将步骤(1)称取的粉末放入混料机内混合30~60min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加200~300MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至6~8Pa后进行烧结,以50~100℃/min的升温速度,加热至950~1000℃的烧结温度后保温5~8min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
本发明步骤(1)中,锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径10~30nm。
本发明步骤(1)中,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为1%~10%。
本发明步骤(1)中,碳酸氢铵的纯度为分析纯,平均粒径500~1000μm。
优选的,本发明所述定制不锈钢模具包括压头1、模体2、模腔3、底座4,模体2的下端设有底座4,模体2内均匀分布有4~6个模腔3,模腔3为长方体形状。
与现有技术相比,本发明的优点在于:
(1)材料成分纯净无有害杂质,生物相容性好。由于在制备过程中不添加任何粘结剂和模板剂,选择的NH4HCO3造孔剂在较低的温度下就完全挥发,因而制备的骨修复用多孔锶掺杂羟基磷灰石材料无任何杂质残留,并且采用了放电等离子烧结技术后降低了烧结温度和保温时间,HA不会发生分解。
(2)孔隙参量可控,成骨活性好。所制备的多孔材料孔隙率为20~40%、孔隙尺寸为10~500μm,且大孔、小孔并存,其独特的孔隙结构和粗糙的内外表面将有利于成骨细胞的粘附、增殖,促使新骨组织长入孔隙,提高了材料的成骨活性。
(3)具有良好的成骨诱导能力。由于掺杂了具有促进成骨和抑制破骨作用的锶(Strontium,简称Sr)元素,提高了多孔HA骨修复材料的成骨诱导能力,加快了骨缺损修复的过程和时间,减少了病人的痛苦。
(4)具有骨修复填充术所需的机械强度。所制备的多孔材料强度为6~8MPa,与自体骨相匹配,能够满足临床要求;因此,采用本发明方法制备的骨修复用多孔锶掺杂羟基磷灰石材料可作为理想的人造机体硬组织再生或重建的骨缺损修复材料在临床上应用;同时本发明方法工艺简单、操作方便、成本低廉,易于实现工业化生产。
附图说明
图1实施例1中Sr-HA原料粉末及1000℃烧结后骨修复用多孔Sr-HA材料的X射线衍射图谱。
图2实施例1制备得到的骨修复用多孔Sr-HA材料表面SEM形貌图。
图3实施例1制备得到的骨修复用多孔Sr-HA材料孔隙SEM形貌图。
图4实施例1制备得到的骨修复用多孔Sr-HA材料孔壁SEM形貌图。
图5实施例1制备得到的骨修复用多孔Sr-HA材料与BMSCs共培养SEM形貌图。
图6为所述定制不锈钢模具的结构示意图。
图7为所述定制不锈钢模具的俯视图。
图6、7中1-压头;2-模体;3-模腔;4-底座。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
本发明实施例所述定制不锈钢模具包括压头1、模体2、模腔3、底座4,模体2的下端设有底座4,模体2内均匀分布有4个模腔3,模腔3为长方体形状,如图6~7所示。
实施例1
本例用放电等离子烧结制备骨修复用多孔Sr-HA材料方法的工艺步骤是:
(1)按锶掺杂羟基磷灰石50%、碳酸氢铵50%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末;锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径10nm,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为1%,碳酸氢铵的纯度为分析纯,平均粒径500μm。
(2)将步骤(1)称取的粉末放入混料机内混合30min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加200MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至8Pa后进行烧结,以50℃/min的升温速度,加热至1000℃的烧结温度后保温5min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
用相对密度法进行测量、并通过计算获得骨修复用多孔锶掺杂羟基磷灰石材料的孔隙率为40%。对烧结前预先干燥的Sr-HA与HA粉料样品进行了X射线衍射仪(XRD)分析(如图1所示)。从图中可以看出,图谱中并无杂相出现,烧结后主相仍为Sr-HA相,这表明烧结完成后试样并未发生分解,有利于保持骨修复用多孔锶掺杂羟基磷灰石材料的生物相容性。利用扫描电镜(SEM)对所烧结的骨修复用多孔锶掺杂羟基磷灰石材料微观形貌进行了分析(如图2、图3、图4所示)。观察孔隙形貌(如图2、图3所示),试样的孔呈均匀的分布状态,孔径在70~400μm范围,这种大孔是由于造孔剂在烧结过程中高温分解而造成的,这样的孔有利于骨细胞的长入和体液的传输;观察孔壁形貌(如图4所示),孔壁上存在由大量的掺锶羟基磷灰石颗粒堆积形成的微孔(<10μm),这些微孔使材料局部面积大大增加,有利于成骨细胞的黏附(如图5所示)。根据GB/T1964-1996在力学试验机上测试了试样的压缩性能,结果表明材料的抗压强度在6MPa,可满足临床上对生物骨修复材料力学性能的要求。
上述结果表明,利用该方法在不添加任何粘结剂和模板剂的情况下制备出的骨修复用多孔Sr-HA材料具有成分纯净、孔隙率可控、孔结构有利于成骨细胞在其表面粘附生长等优点,并且工艺简单、操作方便、成本低廉,适宜用作人体骨修复材料。
实施例2
本例用放电等离子烧结制备骨修复用多孔Sr-HA材料方法的工艺步骤是:
(1)按锶掺杂羟基磷灰石80%、碳酸氢铵20%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末,锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径30nm,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为10%,碳酸氢铵的纯度为分析纯,平均粒径1000μm;
(2)将步骤(1)称取的粉末放入混料机内混合40min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加220MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至8Pa后进行烧结,以60℃/min的升温速度,加热至950℃的烧结温度后保温8min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
按本例中相同的工艺条件,分别按锶掺杂羟基磷灰石60%、NH4HCO340%,锶掺杂羟基磷灰石70%、NH4HCO330%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末。
结果表明所制备骨修复用多孔Sr-HA材料的孔隙率分别为20%、25%、35%,抗压强度分别为8MPa、7.5MPa、7MPa,具有较好的孔隙率和良好的力学性能,可满足临床上对生物骨修复材料性能的要求。
实施例3
本例用放电等离子烧结制备骨修复用多孔Sr-HA材料方法的工艺步骤是:
(1)按锶掺杂羟基磷灰石50%、碳酸氢铵50%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末,锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径20nm,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为5%,碳酸氢铵的纯度为分析纯,平均粒径800μm;
(2)将步骤(1)称取的粉末放入混料机内混合50min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加240MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至8Pa后进行烧结,以80℃/min的升温速度,加热至980℃的烧结温度后保温6min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
按本例中相同的工艺条件,分别以锶掺杂量质量百分比3%,7%,10%的锶掺杂羟基磷灰石为原料。结果表明所制备各组骨修复用多孔Sr-HA材料的孔隙率均约为40%,抗压强度分别为7.2MPa、6.5MPa、6.2MPa、5.6MPa,具有较好的孔隙率和良好的力学性能,可满足临床上对生物骨修复材料性能的要求。
实施例4
本例用放电等离子烧结制备骨修复用多孔Sr-HA材料方法的工艺步骤是:
(1)按锶掺杂羟基磷灰石50%、碳酸氢铵50%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末,锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径30nm,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为5%,碳酸氢铵的纯度为分析纯,平均粒径500μm;
(2)将步骤(1)称取的粉末放入混料机内混合30min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加300MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至8Pa后进行烧结,以100℃/min的升温速度,加热至1000℃的烧结温度后保温5min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
按本例中相同的工艺条件,混合后的粉末分别经过250Mpa,270Mpa加压成型。结果表明所制备骨修复用多孔Sr-HA材料的孔隙率分别为30%、25%、20%,抗压强度分别为7MPa、7.5MPa、8MPa,具有较好的孔隙率和良好的力学性能,可满足临床上对生物骨修复材料性能的要求。
实施例5
本例用放电等离子烧结制备骨修复用多孔Sr-HA材料方法的工艺步骤是:
(1)按锶掺杂羟基磷灰石50%、碳酸氢铵50%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末,锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径10nm,锶掺杂羟基磷灰石中锶掺杂量的质量百分比为5%,碳酸氢铵的纯度为分析纯,平均粒径500μm;
(2)将步骤(1)称取的粉末放入混料机内混合30min,得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末;
(3)将步骤(2)得到的混合粉末放入定制不锈钢模具中,通过压头施加200MPa单向压力,冷压成型后退模得到块体压坯。
(4)将步骤(3)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至8Pa后进行烧结,以50℃/min的升温速度,加热至950℃的烧结温度后保温5min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
按本例中相同的工艺条件,将混合后的粉末分别在960、970℃进行烧结。结果表明所制备骨修复用多孔Sr-HA材料的孔隙率分别为40%、38%、35%,抗压强度分别为6MPa、6.4MPa、7MPa,具有较好的孔隙率和良好的力学性能,可满足临床上对生物骨修复材料性能的要求。
Claims (6)
1.一种骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于,具体包括以下步骤:
(1)按锶掺杂羟基磷灰石50%~80%、碳酸氢铵50%~20%的质量百分比,分别称取锶掺杂羟基磷灰石粉末和碳酸氢铵粉末,然后将锶掺杂羟基磷灰石粉末和碳酸氢铵粉末混合均匀得到锶掺杂羟基磷灰石和碳酸氢铵的混合粉末,碳酸氢铵粉末的平均粒径500~1000μm;
(2)将步骤(1)得到的混合粉末放入定制不锈钢模具中冷压成型后退模得到块体压坯;
(3)将步骤(2)得到的块体压坯装入柱形石墨模具中,置于放电等离子烧结炉中,系统真空抽至6~8Pa后进行烧结,以50~100℃/min的升温速度,加热至950~1000℃的烧结温度后保温5~8min,烧结过程中持续抽真空使得碳酸氢铵完全分解挥发后再随炉自然冷却至室温,退模即得到骨修复用多孔锶掺杂羟基磷灰石材料。
2.根据权利要求1所述的骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于:步骤(1)中锶掺杂羟基磷灰石的纯度≥99.9%,平均粒径10~30nm。
3.根据权利要求1或2所述的骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于:步骤(1)中锶掺杂羟基磷灰石中锶掺杂量的质量百分比为1%~10%。
4.根据权利要求1所述的骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于:锶掺杂羟基磷灰石粉末和碳酸氢铵粉末混合过程为放入混料机内混合30~60min。
5.根据权利要求1所述的骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于:步骤(2)所述冷压成型通过压头施加200~300MPa单向压力。
6.根据权利要求1所述的骨修复用多孔锶掺杂羟基磷灰石材料的制备方法,其特征在于:所述定制不锈钢模具包括压头(1)、模体(2)、模腔(3)、底座(4),模体(2)的下端设有底座(4),模体(2)内均匀分布有4~6个模腔(3),模腔(3)为长方体形状。
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