CN105712736A - 一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法 - Google Patents
一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法 Download PDFInfo
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- CN105712736A CN105712736A CN201610063510.2A CN201610063510A CN105712736A CN 105712736 A CN105712736 A CN 105712736A CN 201610063510 A CN201610063510 A CN 201610063510A CN 105712736 A CN105712736 A CN 105712736A
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- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 88
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 80
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 43
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 35
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 32
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 32
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 239000002002 slurry Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 208000002925 dental caries Diseases 0.000 claims description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims 1
- 229940043256 calcium pyrophosphate Drugs 0.000 claims 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 8
- 230000002188 osteogenic effect Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000017423 tissue regeneration Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000003519 biomedical and dental material Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000011224 oxide ceramic Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 230000006735 deficit Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000009418 renovation Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
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- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 208000010392 Bone Fractures Diseases 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000001582 osteoblastic effect Effects 0.000 description 2
- 230000002138 osteoinductive effect Effects 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
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- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 210000004271 bone marrow stromal cell Anatomy 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- DKJCUVXSBOMWAV-PCWWUVHHSA-N naltrindole Chemical compound N1([C@H]2CC3=CC=C(C=4O[C@@H]5[C@](C3=4)([C@]2(CC2=C3[CH]C=CC=C3N=C25)O)CC1)O)CC1CC1 DKJCUVXSBOMWAV-PCWWUVHHSA-N 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- -1 strontium oxide (SrO) compound Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
本发明涉及一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,属于生物医用材料制备技术领域。将羟基磷灰石(88%~99%)与氧化锶(12%~1%)陶瓷粉末按质量比称取后进行球磨得到混合粉末,然后按混合粉末(40%~70%)与碳酸氢铵造孔剂粉末(60%~30%)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,退模即得到多孔羟基磷灰石/氧化锶复合骨修复材料。利用本发明制备多孔羟基磷灰石/氧化锶复合骨修复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20~50%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,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
本发明涉及一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,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,其中自体骨是最为理想的骨缺损修复材料,但是存在来源不足、供骨区并发症等问题,限制了其应用;而同种异体骨存在移植排异反应、疾病传播及融合时间较长等问题。因此,需要研究和开发新型人工骨修复材料以满足临床上的大量需求。
对于生物医用骨修复材料,应具备以下特性:(1)无组织危害性且具有良好的生物相容性;(2)良好的成骨诱导活性;(3)与骨置换;(4)具有骨修复填充术所需的机械强度。上述特性是评价人工骨修复材料临床应用性能的关键指标。基于以上要求,羟基磷灰石(Hydroxyapatite,Ca10(PO4)6(OH)2,简称HA)特别是互连多孔的HA骨修复材料由于具有上述性能,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多孔羟基磷灰石/氧化锶复合骨修复材料的方法,获得成分纯净无有害杂质、孔隙率可控、具有良好成骨诱导能力的多孔羟基磷灰石/氧化锶复合骨修复材料,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,实现其临床应用。
本发明的技术方案是:一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,经过下列工艺步骤:
(1)按羟基磷灰石88%~99%、氧化锶12%~1%的质量百分比分别称取羟基磷灰石粉末、氧化锶粉末,备用;
(2)将羟基磷灰石粉末、氧化锶粉末进行球磨混粉后得到混合粉末A;
(3)将步骤(2)得到的混合粉末A、碳酸氢铵粉末混合均匀得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B,在混合粉末B中混合粉末A的质量百分比为40%~70%、碳酸氢铵的质量百分比为60%~30%,碳酸氢铵粉末的平均粒径300~500μm;
(4)将步骤(3)得到的混合粉末B放入定制不锈钢模具中,冷压成型后退模得到块体压坯;
(5)将步骤(4)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2~6Pa后进行烧结,以50~100℃/min的升温速度,加热至1000~1100℃的烧结温度后保温3~5min,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,退模即得到多孔羟基磷灰石/氧化锶复合骨修复材料。
优选的,本发明所述羟基磷灰石的纯度≥99.7%,平均粒径为10~100nm。
优选的,本发明所述氧化锶粉末的纯度≥99.9%、平均粒径5~20μm。
优选的,本发明步骤(2)中所述球磨混粉过程为:将羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,加入玛瑙磨球和无水乙醇,然后进行球磨混粉3~5h,将球磨后的浆料干燥后进行研磨,得到混合粉末A。
优选的,本发明步骤(2)中所述混合粉末A、碳酸氢铵粉末的混合过程为,将混合粉末A、碳酸氢铵粉末放入混料机内混合30~60min。
优选的,本发明所述冷压成型压头施加150~200MPa的单向压力。
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,因而制备的羟基磷灰石/氧化锶复合骨修复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)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;
(3)孔隙参量可控,成骨活性好。所制备的多孔材料孔隙率为20~50%、孔隙尺寸为20~1000μm,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;
(4)具有良好的成骨诱导能力。由于通过羟基磷灰石与氧化锶(SrO)复合的方式加入了具有促进成骨和抑制破骨作用的锶(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,能够提高治疗效果。
因此,采用本发明方法制备的多孔羟基磷灰石/氧化锶复合骨修复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所述HA原料粉末、HA/SrO混合粉末及1100℃烧结后的多孔HA/SrO复合骨修复材料的X射线衍射图谱。
图2实施例1得到的多孔HA/SrO复合骨修复材料宏观SEM形貌图。
图3实施例1得到的多孔HA/SrO复合骨修复材料孔隙SEM形貌图。
图4实施例1得到的多孔HA/SrO复合骨修复材料孔壁SEM形貌图。
图5实施例1得到的多孔HA/SrO复合骨修复材料与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6~7所示。
实施例1
本例用放电等离子烧结制备多孔HA/SrO复合骨修复材料方法的工艺步骤是:
(1)按羟基磷灰石99%、氧化锶1%的质量百分比,分别称取纯度≥99.7%、平均粒径100nm的羟基磷灰石和纯度≥99.7%、平均粒径5μm的氧化锶粉末;
(2)将步骤(1)称取的羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,按球料比3:1加入玛瑙磨球,再加入无水乙醇,然后进行球磨混粉3h,将球磨后的浆料干燥后进行研磨,得到混合粉末A;
(3)按步骤(2)得到的混合粉末A70%、碳酸氢铵30%的质量百分比,分别称取混合粉末A和纯度为分析纯、平均粒径300μm的碳酸氢铵粉末;
(4)将步骤(3)称取的粉末放入混料机内混合30min,得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B;
(5)将步骤(4)得到的混合粉末B放入定制不锈钢模具中,通过压头施加150MPa单向压力,冷压成型后退模得到块体压坯。
(6)将步骤(5)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2Pa后进行烧结,以50℃/min的升温速度,加热至1000℃烧结温度后保温3min,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,退模即得到多孔HA/SrO复合骨修复材料。
用相对密度法进行测量、并通过计算获得多孔HA/SrO复合骨修复材料的孔隙率约为20%,对HA原料粉末、HA/SrO混合粉末及1100℃烧结后的多孔HA/SrO复合骨修复材料进行了X射线衍射仪(XRD)分析(如图1所示)。从图中可以看出,图谱中无杂相出现,烧结后主相仍为HA/SrO相,这表明烧结完成后试样并未发生分解,有利于保持多孔HA/SrO复合骨修复材料的生物相容性。利用扫描电镜(SEM)对所烧结的多孔HA/SrO陶瓷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4所示),试样孔壁上存在由大量的HA/SrO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。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,并且在体外细胞共培养实验中表现出良好的细胞相容性(如图5所示),可满足临床上对生物骨修复材料性能的要求。
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多孔HA/SrO复合骨修复材料具有成分纯净、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多孔HA/SrO复合骨修复材料方法的工艺步骤是:
(1)按羟基磷灰石90%、氧化锶10%的质量百分比,分别称取纯度≥99.7%、平均粒径100nm的羟基磷灰石和纯度≥99.7%、平均粒径10μm的氧化锶粉末;
(2)将步骤(1)称取的羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,按球料比3:1加入玛瑙磨球,再加入无水乙醇,然后进行球磨混粉3h,将球磨后的浆料干燥后进行研磨,得到混合粉末A;
(3)按步骤(2)得到的混合粉末A50%、碳酸氢铵50%的质量百分比,分别称取混合粉末A和纯度为分析纯、平均粒径400μm的碳酸氢铵粉末;
(4)将步骤(3)称取的粉末放入混料机内混合40min,得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B;
(5)将步骤(4)得到的混合粉末B放入定制不锈钢模具中,通过压头施加180MPa单向压力,冷压成型后退模得到块体压坯。
(6)将步骤(5)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4Pa后进行烧结,以100℃/min的升温速度,加热至1100℃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,退模即得到多孔HA/SrO复合骨修复材料。
结果表明本实施例制备得到的多孔HA/SrO复合骨修复材料孔隙率为35%,抗压强度为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3
本例用放电等离子烧结制备多孔HA/SrO复合骨修复材料方法的工艺步骤是:
(1)按羟基磷灰石95%、氧化锶5%的质量百分比,分别称取纯度≥99.7%、平均粒径80nm的羟基磷灰石和纯度≥99.7%、平均粒径15μm的氧化锶粉末;
(2)将步骤(1)称取的羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,按球料比3:1加入玛瑙磨球,再加入无水乙醇,然后进行球磨混粉5h,将球磨后的浆料干燥后进行研磨,得到混合粉末A;
(3)按步骤(2)得到的混合粉末A40%、碳酸氢铵60%的质量百分比,分别称取混合粉末A和纯度为分析纯、平均粒径500μm的碳酸氢铵粉末;
(4)将步骤(3)称取的粉末放入混料机内混合50min,得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B;
(5)将步骤(4)得到的混合粉末B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。
(6)将步骤(5)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80℃/min的升温速度,加热至1050℃的烧结温度后保温4min,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,退模即得到多孔HA/SrO复合骨修复材料。
结果表明本实施例制备得到的多孔HA/SrO复合骨修复材料孔隙率为20%,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4
本例用放电等离子烧结制备多孔HA/SrO复合骨修复材料方法的工艺步骤是:
(1)按羟基磷灰石88%、氧化锶12%的质量百分比,分别称取纯度≥99.7%、平均粒径20nm的羟基磷灰石和纯度≥99.7%、平均粒径20μm的氧化锶粉末;
(2)将步骤(1)称取的羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,按球料比3:1加入玛瑙磨球,再加入无水乙醇,然后进行球磨混粉4h,将球磨后的浆料干燥后进行研磨,得到混合粉末A;
(3)按步骤(2)得到的混合粉末A60%、碳酸氢铵40%的质量百分比,分别称取混合粉末A和纯度为分析纯、平均粒径450μm的碳酸氢铵粉末;
(4)将步骤(3)称取的粉末放入混料机内混合60min,得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B;
(5)将步骤(4)得到的混合粉末B放入定制不锈钢模具中,通过压头施加170MPa单向压力,冷压成型后退模得到块体压坯。
(6)将步骤(5)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5Pa后进行烧结,以60℃/min的升温速度,加热至1080℃的烧结温度后保温3min,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,退模即得到多孔HA/SrO复合骨修复材料。
结果表明本实施例制备得到的多孔HA/SrO复合骨修复材料孔隙率为40%,抗压强度为5.5MPa,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。
Claims (7)
1.一种多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于,具体包括以下工艺步骤:
(1)按羟基磷灰石88%~99%、氧化锶12%~1%的质量百分比分别称取羟基磷灰石粉末、氧化锶粉末,备用;
(2)将羟基磷灰石粉末、氧化锶粉末进行球磨混粉后得到混合粉末A;
(3)将步骤(2)得到的混合粉末A、碳酸氢铵粉末混合均匀得到羟基磷灰石、氧化锶、碳酸氢铵混合粉末B,在混合粉末B中混合粉末A的质量百分比为40%~70%、碳酸氢铵的质量百分比为60%~30%,碳酸氢铵粉末的平均粒径为300~500μm;
(4)将步骤(3)得到的混合粉末B放入定制不锈钢模具中,冷压成型后退模得到块体压坯;
(5)将步骤(4)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2~6Pa后进行烧结,以50~100℃/min的升温速度,加热至1000~1100℃的烧结温度后保温3~5min,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,退模即得到多孔羟基磷灰石/氧化锶复合骨修复材料。
2.根据权利要求1所多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于:所述羟基磷灰石的纯度≥99.7%,平均粒径为10~100nm。
3.根据权利要求1所述多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于:所述氧化锶粉末的纯度≥99.9%、平均粒径为5~20μm。
4.根据权利要求1所述多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于:步骤(2)中所述球磨混粉过程为:将羟基磷灰石粉末、氧化锶粉末放入球磨机玛瑙球磨罐中,加入玛瑙磨球和无水乙醇,然后进行球磨混粉3~5h,将球磨后的浆料干燥后进行研磨,得到混合粉末A。
5.根据权利要求1所述多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于:步骤(2)中所述混合粉末A、碳酸氢铵粉末的混合过程为,将混合粉末A、碳酸氢铵粉末放入混料机内混合30~60min。
6.根据权利要求1所述多孔羟基磷灰石/氧化锶复合骨修复材料的制备方法,其特征在于:所述冷压成型压头施加150~200MPa的单向压力。
7.根据权利要求1所述多孔羟基磷灰石/焦磷酸钙复合骨修复材料的制备方法,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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