CN105712735A - 一种骨修复用多孔羟基磷灰石材料的制备方法 - Google Patents
一种骨修复用多孔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。将羟基磷灰石粉末(25%~50%)与碳酸氢铵造孔剂粉末(75%~50%)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羟基磷灰石材料。利用本发明制备骨修复用多孔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40~70%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
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)。HA生物陶瓷材料因具有与人体骨骼晶体成分和结构基本一致,生物相容性、界面活性及骨传导性均优于各类医用合金、橡胶及其它高分子材料,并且能够与骨直接形成键性结合等优点,成为当前临床上人造生物骨修复材料的理想选择之一。生物研究和临床应用表明,临床上需要的骨缺损修复材料不仅要具有合适的力学性能,还希望具有与人体骨组织相似的互连多孔结构。互连多孔的羟基磷灰石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度,而且还能满足骨组织及血管的长入,加快骨缺损修复的过程。国内外相关研究结果表明,多孔羟基磷灰石骨修复材料中含有适当尺寸并占有一定体积分数的孔隙(一般希望孔隙率大于40%,大孔与微孔并存,大孔孔径100-300μm)能为细胞、纤维组织和骨组织的长入提供通道和生长空间,增大组织液与羟基磷灰石接触表面积,并通过影响代谢、营养传输和血管生长而决定骨长入的程度和速度,加快骨修复过程。
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。
发明内容
本发明的目的在于针对现有骨修复用多孔羟基磷灰石材料制备技术的不足,提供一种利用放电等离子烧结制备骨修复用多孔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、具有良好成骨诱导活性的骨修复用多孔羟基磷灰石材料,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:一种骨修复用多孔羟基磷灰石材料的制备方法,经过下列工艺步骤:
(1)按羟基磷灰石25%~50%、碳酸氢铵75%~50%的质量百分比,分别称取羟基磷灰石粉末和碳酸氢铵粉末,混合均匀(放入混料机内混合30~45min)后得到羟基磷灰石和碳酸氢铵的混合粉末。
(2)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200~500MPa单向压力,冷压成型后退模得到块体压坯。
(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200~500MPa单向压力,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100~150℃/min的升温速度,加热至800~900℃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羟基磷灰石材料。
本发明步骤(1)中,羟基磷灰石的纯度≥97%,平均粒径10~30nm。
本发明步骤(1)中,碳酸氢铵的纯度为分析纯,平均粒径500~800μm。
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40~70%、孔隙尺寸为100~1000μm,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)具有骨修复填充术所需的机械强度。所制备的多孔材料强度为4~6MPa,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900℃烧结后骨修复用多孔HA材料的X射线衍射图谱。
图2实施例1中900℃烧结后骨修复用多孔HA材料孔隙SEM形貌图。
图3实施例1中900℃烧结后骨修复用多孔HA材料孔壁SEM形貌图。
图4实施例1中900℃烧结后骨修复用多孔HA材料与BMSCs共培养SEM形貌图。
图5为所述定制不锈钢模具的结构示意图。
图6为所述定制不锈钢模具的俯视图。
图5、6中1-压头;2-模体;3-模腔;4-底座。
具体实施方式
下面结合附图和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5~6所示。
实施例1
本例用放电等离子烧结制备骨修复用多孔HA材料的工艺步骤是:
(1)按羟基磷灰石50%、碳酸氢铵50%的质量百分比,分别称取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30min,得到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100℃/min的升温速度,加热至900℃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HA材料的孔隙率为40%。对烧结后骨修复用多孔HA材料样品进行了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HA相,这表明烧结完成后试样并未发生分解,有利于保持烧结后骨修复用多孔HA材料的生物相容性。利用扫描电镜(SEM)对所烧结的烧结后骨修复用多孔HA材料微观形貌进行了分析(如图2、图3所示),观察孔隙形貌(如图2所示),试样中孔隙呈均匀的分布状态,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3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4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HA材料方法的工艺步骤是:
(1)按羟基磷灰石25%、碳酸氢铵75%的质量百分比,分别称取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35min,得到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6Pa后进行烧结,以150℃/min的升温速度,加热至820℃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羟基磷灰石材料。
结果表明所制备骨修复用多孔HA材料的孔隙率为70%、抗压强度为4MPa,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HA材料方法的工艺步骤是:
(1)按羟基磷灰石40%、碳酸氢铵60%的质量百分比,分别称取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40min,得到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400MPa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7Pa后进行烧结,以110℃/min的升温速度,加热至800℃的烧结温度后保温7min,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羟基磷灰石材料。
结果表明所制备骨修复用多孔HA材料的孔隙率为50%、抗压强度为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HA材料方法的工艺步骤是:
(1)按羟基磷灰石30%、碳酸氢铵70%的质量百分比,分别称取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45min,得到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500MPa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120℃/min的升温速度,加热至850℃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羟基磷灰石材料。
结果表明所制备骨修复用多孔HA材料的孔隙率为60%、抗压强度为4.5MPa,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HA材料方法的工艺步骤是:
(1)按羟基磷灰石35%、碳酸氢铵65%的质量百分比,分别称取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30min,得到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450MPa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7.5Pa后进行烧结,以130℃/min的升温速度,加热至880℃的烧结温度后保温7.5min,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羟基磷灰石材料。
结果表明所制备骨修复用多孔HA材料的孔隙率为55%、抗压强度为4.8MPa,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。
Claims (6)
1.一种骨修复用多孔羟基磷灰石材料的制备方法,其特征在于,具体包括以下工艺步骤:
(1)按羟基磷灰石25%~50%、碳酸氢铵75%~50%的质量百分比,分别称取羟基磷灰石粉末和碳酸氢铵粉末,混合均匀后得到羟基磷灰石和碳酸氢铵的混合粉末;
(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100~150℃/min的升温速度,加热至800~900℃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羟基磷灰石材料。
2.根据权利要求1所述的骨修复用多孔羟基磷灰石材料的制备方法,其特征在于:步骤(1)中羟基磷灰石的纯度≥97%,平均粒径10~30nm。
3.根据权利要求1所述的骨修复用多孔羟基磷灰石材料的制备方法,其特征在于:步骤(1)中碳酸氢铵的纯度为分析纯,平均粒径500~800μm。
4.根据权利要求1所述的骨修复用多孔羟基磷灰石材料的制备方法,其特征在于:步骤(1)所述混合过程为将羟基磷灰石粉末和碳酸氢铵粉末放入混料机内混合30~45min。
5.根据权利要求1所述的骨修复用多孔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的单向压力为200~500MPa。
6.根据权利要求1所述的骨修复用多孔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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