CN110054491A - 一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法 - Google Patents
一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法 Download PDFInfo
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- CN110054491A CN110054491A CN201910237059.5A CN201910237059A CN110054491A CN 110054491 A CN110054491 A CN 110054491A CN 201910237059 A CN201910237059 A CN 201910237059A CN 110054491 A CN110054491 A CN 110054491A
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 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 38
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 34
- 239000003462 bioceramic Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 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 abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 abstract description 17
- 230000002188 osteogenic effect Effects 0.000 abstract description 6
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- 230000008439 repair process Effects 0.000 abstract description 2
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- 238000007906 compression Methods 0.000 description 5
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- 239000011701 zinc Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
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- 229910052725 zinc Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010005949 Bone cancer Diseases 0.000 description 1
- 206010056377 Bone tuberculosis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000009360 Osteoarticular Tuberculosis Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002491 angiogenic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 210000001124 body fluid Anatomy 0.000 description 1
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- 238000005297 material degradation process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,属于生物医用材料制备技术领域。本发明所述方法以纳米锌粉末和羟基磷灰石粉末为原料,按照质量比ZnO:HA=1~7%:99%~93%进行称取,然后进行球磨后得到复合粉末,将复合粉末与造孔剂碳酸氢铵进行混合,混合均匀后经过压制得到坯体,利用放电等离子烧结方法制备出纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷;本发明制备出的多孔生物陶瓷不仅成分纯净,材料的孔隙率可以达到40~70%且可控,而且纳米氧化锌的加入,能提高多孔生物陶瓷的成骨诱导能力,从而提高植入部位周围的骨形成能力;通过控制材料的孔隙率,可以制备出不同需求的生物陶瓷,适用于骨支架、填充和修复材料。
Description
技术领域
本文涉及一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,属于生物医用材料制备技术领域。
背景技术
近年来,随着我国国民经济快速发展、人民生活水平提高、人口日益老龄化以及医疗卫生水平的显著提高,由于工伤、交通事故、骨肿瘤、骨结核等疾病导致的骨科患者越来越多。目前临床上应用的人工骨材料存在植骨延迟愈合或不愈合、人工骨的降解与成骨速率不匹配、植骨材料碎裂变形、植骨后塌陷致骨块高度丢失、植骨后感染、长期窦道形成、植骨部位长期疼痛等问题。
现有技术制备的多孔羟基磷灰石基人工骨材料,存在以下问题:(1)为了提高材料的力学性能和获得稳定多孔结构,需要对材料进行较长时间的高温烧结过程。过高的烧结温度和较长的保温时间会造成羟基磷灰石发生部分分解,导致材料生物活性下降;(2)在制备材料过程中需要加入粘结剂(如聚乙烯醇、硅酸钠等),高温烧结后有少量残留。残留的粘结剂不会降解,降低了材料的生物活性和成骨活性,甚至产生毒性;(3)应用过程中材料的降解与成骨速率不匹配,促进成骨的材料与元素作用有限,容易导致植入后植骨延迟愈合或不愈合。
发明内容
本发明的目的在提供一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,将可降解的活性纳米氧化锌掺入多孔羟基磷灰石中,利用放电等离子烧结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纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷,满足临床上对用于机体硬组织再生或重建的人工骨材料的性能要求。
为了达到上述目的,本发明采用的技术方案是:
一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,具体包括以下步骤:
(1)将纳米氧化锌和纳米羟基磷灰石粉末球磨混合均匀后进行烘干,得到纳米氧化锌掺杂羟基磷灰石复合粉末,复合粉末中纳米氧化锌的质量百分比为1%~7%,纳米羟基磷灰石粉末的质量百分比为99%~93%。
(2)将步骤(1)得到的复合粉末与造孔剂碳酸氢铵粉末混合后得到混合粉末,混合粉末中复合粉末的质量百分比为50%~75%,碳酸氢铵粉末的质量百分比为50%~25%。
(3)将步骤(2)得到的混合粉末放入模具中,冷等静压压制成圆柱状坯体。
(4)将步骤(3)得到的圆柱坯体装入石墨模具中,放入放电等离子烧结炉中进行烧结,将系统抽2~6Pa真空后,持续充入保护气体,首先以100℃/min的升温速度升温至100℃后保温1~2min,随后以50℃/min的速度升温至950~1050℃后保温5~10min,烧结完成后随炉冷却至室温,退模得到纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷。
优选的,本发明所述纳米氧化锌的纯度≥99.9%、粒径为50~60nm,纳米羟基磷灰石粉末的纯度≥99.7%、粒径80~100nm。
优选的,本发明所述球磨的过程为:将称取的粉末原料放入玛瑙球磨罐中,加入玛瑙磨球、无水乙醇和分散剂聚乙二醇,放置于行星球磨机上,经过6~8h球磨,玛瑙磨球球料质量比为3:1~3:2,大中小球质量比1:3:6~1:4:7,分散剂加入量为原料粉末质量的0.5%。
优选的,本发明所述烘干条件为在真空干燥箱中烘干,烘干温度为40~60℃。
优选的,本发明所述碳酸氢铵粉末的纯度为分析纯,平均粒径100~500μm。
优选的,本发明步骤(3)中冷等静压的压力为35~40KN。
优选的,本发明所述保护气体为纯度99.999%的氩气,流速为60ml/min~80 ml/min。
与现有技术相比,本发明的有益效果:
(1)本发明材料成分纯净,无有害杂质。选择的碳酸氢铵在较低的烧结温度下就完全挥发,不存在任何残留;采用放电等离子烧结技术可以降低烧结温度,避免温度过高而造成锌元素的流失,还能减少保温时间,避免煅烧时间过长而造成羟基磷灰石的分解。
(2)材料可以根据需求的不同,通过调整复合粉末与造孔剂的比例,可以得到不同孔隙率、不同强度的生物陶瓷,可用于骨支架、填充和修复材料。多孔材料的孔隙率为40~60%,孔隙尺寸为20~500μm,大小孔并存,独特的孔隙结构与粗糙的内外表面有利于成骨细胞的粘附、增殖,促使骨组织的长入,提高材料的成骨活性。
(3)具有良好的成骨诱导能力。将可降解活性纳米氧化锌掺杂入多孔羟基磷灰石,提高HA基多孔生物陶瓷的成骨诱导能力,提高植入部位周围的骨形成能力,提高治疗效果;纳米氧化锌在体液中存在降解,从而释放出所需要的锌离子,另外氧化锌的加入还能提高材料的力学强度。
附图说明
图1 实施例4制备的纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的X射线衍射图谱;
图2实施例4制备的纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的表面形貌;
图3实施例4制备的纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的矿化形貌图;
图4 实施例4制备的纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的降解性能。
具体实施方式
下面结合具体实施方式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。
实施例1
(1)以纯度≥99.9%、粒径为60nm的纳米氧化锌和纯度≥99.7%、粒径100nm的纳米羟基磷灰石粉末为原料,按质量比1%:99%的分别称取纳米氧化锌和纳米羟基磷灰石粉末。
(2)将步骤(1)称取的粉末原料放入玛瑙球磨罐中,加入玛瑙磨球、无水乙醇和分散剂聚乙二醇(聚乙二醇的加入量为原料粉末质量的0.7%,玛瑙磨球球料质量比为3:1,大中小球质量比1:3:6),放置于行星球磨机上,经过6h球磨,在真空干燥箱中使用60℃烘干研磨后得到纳米氧化锌掺杂羟基磷灰石复合粉末。
(3)将步骤(2)得到的纳米氧化锌掺杂羟基磷灰石复合粉末与纯度AR、平均粒径500μm造孔剂碳酸氢铵粉末按质量比75:25均匀混合后得到混合粉末。
(4)将步骤(3)得到的混合粉末放入模具中,施加40KN的压力,冷等静压制成圆柱状坯体。
(5)将步骤(4)得到的圆柱坯体装入石墨模具中,放入放电等离子烧结炉中进行烧结,将系统抽6Pa真空后,持续充入纯度99.999% 、流速60ml/min的氩气进行保护烧结,首先以100℃/min的升温速度升温至100℃后保温1min,随后以50℃/min的速度升温至950℃的烧结温度后保温5min,烧结完成后随炉冷却至室温,退模得到纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷。
实施例2
以纯度≥99.9%、粒径为60nm的纳米氧化锌和纯度≥99.7%、粒径100nm的纳米羟基磷灰石粉末为原料,按质量比3%:97%分别称取纳米氧化锌和纳米羟基磷灰石粉末,其他的工艺步骤与参数跟实施例1一致。
实施例3
以纯度≥99.9%、粒径为60nm的纳米氧化锌和纯度≥99.7%、粒径100nm的纳米羟基磷灰石粉末为原料,按质量比5%:95%分别称取纳米氧化锌和纳米羟基磷灰石粉末,其他的工艺步骤与参数跟实施例1一致。
实施例4
以纯度≥99.9%、粒径为60nm的纳米氧化锌和纯度≥99.7%、粒径100nm的纳米羟基磷灰石粉末为原料,按质量比7%:93%分别称取纳米氧化锌和纳米羟基磷灰石粉末,其他的工艺步骤与参数跟实施例1一致。
对制备的纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷进行X射线衍射仪(XRD)分析(如图1所示)。从图中可以看出,材料以HA为主体,Zn加入并未对峰位产生影响,物质的基本组成并未发生改变,主相仍然是HA;图谱中没有发现HA分解产物CaO与β–Ca3(PO4)2,说明950℃下,HA没有产生分解。另外 XRD 物相分析中未见NH4HCO3的特征峰,所以其在烧结过程中已完全挥发,所制备得到的陶瓷成分明确,安全性得到保障。
利用陶瓷孔隙率分析仪对材料的孔隙率进行测定;根据GB/T 4740-1999标准在力学试验机上测试了材料的抗压强度,具体结果见表1,材料的抗压强度能满足临床上的需要。
表1 不同锌含量下多孔生物陶瓷的孔隙率与抗压强度
利用扫描电镜(SEM)对制备的生物陶瓷形貌进行分析(如图2所示);观察孔隙形貌(如图3所示),制备材料的均具有相互连通的大小孔结构,孔径在50~500μm且分布较均匀。不管是骨支架材料,还是骨填充材料应该具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,小孔孔径10μm以上)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HA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。同时多孔结构使材料比表面积增加,可增加Zn2+在局部的释放浓度,加速新骨生长,增强成骨的能力。纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷浸泡在SBF溶液中,置于37℃的恒温水浴箱中,测试材料的降解性能(如图4所示),发现材料的降解速率一直加快。
实施例5
(1)以纯度≥99.9%、粒径为60nm的纳米氧化锌和纯度≥99.7%、粒径100nm的纳米羟基磷灰石粉末为原料,按质量比7%:97%分别称取纳米氧化锌和纳米羟基磷灰石粉末;
(2)将步骤(1)称取的粉末原料放入玛瑙球磨罐中,加入玛瑙磨球、无水乙醇和分散剂聚乙二醇,放置于行星球磨机上,经过8h球磨,在真空干燥箱中使用60℃烘干研磨后得到纳米氧化锌掺杂羟基磷灰石复合粉末。
(3)将步骤(2)得到的纳米氧化锌掺杂羟基磷灰石复合粉末与纯度AR、平均粒径500μm造孔剂碳酸氢铵粉末按质量比25:75均匀混合后得到混合粉末。
(4)将步骤(3)得到的混合粉末放入模具中,施加40KN的压力,冷等静压制成圆柱状坯体。
(5)将步骤(4)得到的圆柱坯体装入石墨模具中,放入放电等离子烧结炉中进行烧结,将系统抽2Pa真空后,持续充入纯度99.999% 、流速60ml/min的氩气进行保护烧结,首先以100℃/min的升温速度升温至100℃后保温1min,随后以50℃/min的速度升温至1000℃后保温5min,烧结完成后随炉冷却至室温,退模得到纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷。
实施例6
纳米氧化锌掺杂羟基磷灰石复合粉末与纯度AR、平均粒径500μm造孔剂碳酸氢铵粉末按质量比50:50均匀混合后得到混合粉末,其他的工艺步骤与参数跟实施例5一样。
结果表明实施本实例的制备得到的负载纳米锌羟基磷灰石多孔生物陶瓷孔隙率和抗压强度见表2。可以根据用途的不同,改变材料的孔隙率,满足不同的临床需求。
表2 7%氧化锌多孔生物陶瓷不同孔隙率下的抗压强度
Claims (7)
1.一种纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于,具体包括以下步骤:
(1)将纳米氧化锌和纳米羟基磷灰石粉末球磨混合均匀后进行烘干,得到纳米氧化锌掺杂羟基磷灰石复合粉末,复合粉末中纳米氧化锌的质量百分比为1%~7%,纳米羟基磷灰石粉末的质量百分比为99%~93%;
(2)将步骤(1)得到的复合粉末与造孔剂碳酸氢铵粉末混合后得到混合粉末,混合粉末中复合粉末的质量百分比为50%~75%,碳酸氢铵粉末的质量百分比为50%~25%;
(3)将步骤(2)得到的混合粉末放入模具中,冷等静压压制成圆柱状坯体;
(4)将步骤(3)得到的圆柱坯体装入石墨模具中,放入放电等离子烧结炉中进行烧结,将系统抽2~6Pa真空后,持续充入保护气体,首先以100℃/min的升温速度升温至100℃后保温1~2min,随后以50℃/min的速度升温至950~1050℃后保温5~10min,烧结完成后随炉冷却至室温,退模得到纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷。
2.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:纳米氧化锌的纯度≥99.9%、粒径为50~60nm,纳米羟基磷灰石粉末的纯度≥99.7%、粒径80~100nm。
3.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:球磨的过程为:将称取的粉末原料放入玛瑙球磨罐中,加入玛瑙磨球、无水乙醇和分散剂聚乙二醇,放置于行星球磨机上,经过6~8h球磨,玛瑙磨球球料质量比为3:1~3:2,大中小球质量比1:3:6~1:4:7,分散剂加入量为原料粉末质量的0.5%。
4.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:烘干条件为在真空干燥箱中烘干,烘干温度为40~60℃。
5.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:碳酸氢铵粉末的纯度为分析纯,平均粒径100~500μm。
6.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:步骤(3)中冷等静压的压力为35~40KN。
7.根据权利要求1所述纳米氧化锌掺杂羟基磷灰石多孔生物陶瓷的制备方法,其特征在于:保护气体为纯度99.999%的氩气,流速为60ml/min~80 ml/min。
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