CN115703685A - 一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧结方法 - Google Patents

一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧结方法 Download PDF

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CN115703685A
CN115703685A CN202210883374.7A CN202210883374A CN115703685A CN 115703685 A CN115703685 A CN 115703685A CN 202210883374 A CN202210883374 A CN 202210883374A CN 115703685 A CN115703685 A CN 115703685A
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calcium phosphate
shells
porous ceramic
foaming agent
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何文福
许学全
吴世经
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Abstract

本发明涉及一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧结方法，利用含钙废弃物所制备的羟基磷灰石和起泡剂混合，经过两阶段烧结，制成具有医药用途的骨填充材料。

Description

一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧 结方法
技术领域
本发明涉及一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧结方法，通过将羟基磷灰石材料和起泡剂预混合，并利用发泡法及两阶段不同温度及不同时间的加热，得到具备孔洞的双相磷酸钙。
背景技术
羟基磷灰石（Hydroxyapatite, HA）化学式为Ca10(PO4)6(OH)2，理想的钙磷比为1.67，具有优良生物活性、生物兼容性及骨传导性，可与骨组织形成键结，且HA不具毒性，在体内不会产生炎症反应，因此广泛应用于骨缺损修复及替代材料、整形外科填充材料、组织工程支架及药物载体等。
目前已发现许多不同的羟基磷灰石的合成方法，主要可分为液相合成法与固相合成法，其中固相合成法包含固相烧结法及球磨法；液相合成法则包含溶胶-凝胶法、微乳液法、化学沉淀法、水热法、微波辐射法等。
与传统化学药剂所合成的磷灰石相比，天然牡蛎壳具有多种微量元素，如钠、镁、锶等，而这些微量元素是人体骨骼成长所必需的元素。
目前中国台湾地区合成羟基磷灰石仍以化学合成方式为主，然而，使用天然废弃物所合成的羟基磷灰石比化学合成的更具有优良的生物兼容性，可降低与人体软组织如皮肤、肌肉和牙龈的排斥性，使其成为骨科和牙科植入材料的理想成分，近年来已被广泛应用于硬组织修复和运用在包括骨增强、骨修复以及表面涂层应用。
根据中国台湾地区相关部门对废弃物统计数据显示，2007至2017年，中国台湾地区每年平均产生约19万吨的废弃牡蛎壳。
废弃牡蛎壳不仅占空间，且壳上的残肉容易滋生苍蝇，在高温日照下产生恶臭，造成环境污染问题。
过去牡蛎壳主要用于饲料、堆肥及栽培介质，其整体的附加价值并不高。
发明内容
本发明以废弃牡蛎壳为原料制备羟基磷灰石，制备过程通过使其相变为具有双相羟基磷灰石/β-三钙磷酸盐的骨填充材料，可进一步提升废弃牡蛎壳的附加价值，也能降低其所造成的环境污染问题。
根据本发明的目的，使用生物性含钙原料牡蛎壳所合成的羟基磷灰石结晶结构的成分更类似于人骨，因此生物兼容性较高。
根据本发明的实施方式，包含以下步骤:混合转动步骤、烘干步骤、第一阶段烧结步骤及第二阶段烧结步骤。
混合转动步骤，将羟基磷灰石和起泡剂，以10%比90%至90%比10%的比例混合成混合体，并将所述混合体以250至3000 rpm的高速搅拌成泡沫状，其中优选的混合比例为15%比85%至85%比15%。
烘干步骤，将经过上述混合转动步骤的泡沫状混合体，以50-200℃烘干成定型混合体。
第一阶段烧结步骤，将所述定型混合体在300℃至900℃下持温加热1至5小时，其中优选烧结效果的持温条件为温度500℃至800℃加热2至4小时。
第二阶段烧结步骤，将经过第一阶段烧结的定型混合体在900℃至1400℃下持温加热0.1至30小时，得到含有双相磷酸钙多孔陶瓷的骨填充材料，其中优选烧结效果的持温条件为温度1000℃至1200℃加热15至30小时。
根据本发明的实施方式，制备的双相磷酸钙具有孔隙率40-95%及孔洞尺寸50~700μm的物理表征。
根据本发明的实施方式，制备的双相磷酸钙含有羟基磷灰石及β-三钙磷酸盐成分，所述羟基磷灰石含量（体积百分比）为20%至80%，所述β-三钙磷酸盐含量（体积百分比）为20%至80%。
根据本发明的实施方式，可产生大于100 μm和小于100 μm的孔洞，因此满足多孔植入物的应用性，大于100 μm的孔洞可使骨组织向内生长。另外，羟基磷灰石粉末经过烧结形成颈（necking）互相连接，显示粉体已经互相键结，可提供手术操作所需要的强度。
根据本发明的实施方式，所述羟基磷灰石的晶粒尺寸都介于32-146 nm。
根据本发明的实施方式，所述β-三钙磷酸盐的晶粒尺寸都介于37-49 nm。
根据本发明的实施方式，所述羟基磷灰石的结晶度高于62%。
本发明的废弃原料包含但不限于蛋壳、甲壳亚门动物的螃蟹壳、虾壳、龙虾壳、淡水龙虾壳与磷虾壳、双壳纲动物的牡蛎壳、蛤蛎壳、文蛤壳、腹足纲动物的鲍鱼壳。
本发明的另一方面提供一种生物医药材料及制备方法，其包含但不限于骨材料、牙科材料。
本发明的另一方面提供一种含钠、镁、锶的钙磷化合物及其制备方法。
附图说明
图1为双相磷酸钙多孔陶瓷在不同持温时间烧结的（X-Ray Diffractometer,XRD）衍射图。
图2为双相磷酸钙多孔陶瓷在不同持温温度烧结的衍射图。
图3为双相磷酸钙多孔陶瓷在不同持温时间烧结的衍射图。
图4为双相磷酸钙多孔陶瓷的傅里叶变换红外光谱（Fourier-transforminfrared spectroscopy, FTIR）分析。
图5为双相磷酸钙多孔陶瓷的扫描式电子显微镜（Field Emission ScanningElectron Microscope, FESEM）照片。
图6为双相磷酸钙多孔陶瓷的孔径分布。
图7为双相磷酸钙多孔陶瓷浸泡在人工模拟体液（Simulated body fluid, SBF）中的pH变化。
图8为双相磷酸钙多孔陶瓷浸泡在SBF中7天后的FESEM照片。
图9为MTT细胞活性试验。
图10为第1、7、14天D1小鼠前驱干细胞的WST-8细胞活性试验。
图11为第1、7、14天D1小鼠前驱干细胞的ALP骨分化试验。
具体实施方式
根据本发明的优选实施例，将1克羟基磷灰石与1.5 ml起泡剂混合，其中所述起泡剂包含但不限于椰子油起泡剂、葡萄糖起泡剂（癸基葡萄糖甘）、氨基酸起泡剂（TEA CocoylGlutamate）、弱酸性起泡剂（Ammonium Lauryl Sulfate）、月桂酰肌氨酸钠（SodiumLauroyl Sarcosinate）和脂肪醇表面活性剂（Fatty Alcohol Ethoxylate）。
参考图1，其是本发明的双相磷酸钙多孔陶瓷在不同持温时间烧结的XRD衍射图。通过衍射图可得知羟基磷灰石及β-三钙磷酸盐的两相比例、两阶段烧结温度和时间，如下表一所示。
X射线衍射分析是将样品试片研磨成粉状后，用X射线衍射分析仪（XRD；D8，Bruker，Germany）进行相分析。X射线衍射分析仪使用铜靶材（X射线的波长为0.15406 nm），操作电压为30 kV，操作电流为30 mA，设定扫描速度为2°/min，衍射角度为20°–40°。
表一 双相磷酸钙多孔陶瓷在不同持温时间烧结后的相比例、晶粒尺寸及结晶度。
Figure DEST_PATH_IMAGE001
根据本发明优选实施例，将1克羟基磷灰石与1.5 ml起泡剂混合，其中所述起泡剂为椰子油起泡剂。
参考图2，其是本发明的双相磷酸钙多孔陶瓷在不同持温温度烧结的XRD衍射图。通过衍射图可得知羟基磷灰石及β-三钙磷酸盐的两相比例、两阶段烧结温度和时间，如下表二所示。
表二 双相磷酸钙多孔陶瓷在不同持温温度烧结后的相比例、晶粒尺寸及结晶度。
Figure 421704DEST_PATH_IMAGE002
根据本发明优选实施例，将1克羟基磷灰石与1.5 ml起泡剂混合，其中所述起泡剂为椰子油起泡剂。
参考图3，其是本发明的双相磷酸钙多孔陶瓷在不同持温时间烧结的XRD衍射图。通过衍射图可得知羟基磷灰石及β-三钙磷酸盐的两相比例、两阶段烧结温度和时间，如下表三所示。
表三 双相磷酸钙多孔陶瓷在不同持温时间烧结后的相比例、晶粒尺寸及结晶度。
Figure DEST_PATH_IMAGE003
根据本发明的实施方式，羟基磷灰石含量（体积百分比）为20%至80%，β-三钙磷酸盐含量（体积百分比）为20%至80%，其中优选分别为62%与38%。
根据本发明的实施方式，羟基磷灰石的晶粒尺寸都介于32-146 nm，其中优选为38、49、50 nm。
根据本发明的实施方式，β-三钙磷酸盐的晶粒尺寸都介于37-49 nm，其中优选为37、38、49 nm。
根据本发明的实施方式，第一阶段烧结温度和时间为700℃持温2小时、其中优选的第二阶段烧结温度为1000℃，优选的持温烧结时间为25小时，以所述条件进行后续分析。
参考图4，其是本发明的双相磷酸钙多孔陶瓷的FTIR分析结果图。通过官能基比对发现，经过本发明烧结的产物具有双相磷酸钙的化学官能基团，包含OH-和PO4 3-基团。
傅里叶变换红外光谱仪FTIR分析（FTIR；Cary 630，Agilent，Santa Clara，USA）通过典型的KBr颗粒技术分析样品的化学成分，获得波数范围为600–4000 cm-1。
参考图5，其是本发明双相磷酸钙多孔陶瓷的FESEM照片。可以发现经过本发明烧结的结晶颗粒存在多孔性，且许多孔洞大于100 μm，另外可以从照片发现，孔洞之间具有连通性，可以从一侧的孔洞观察到另一侧的孔洞。
FESEM是将样品试片表面镀白金（电流为10 mA，溅镀时间为50秒），利用扫描式电子显微镜（FESEM；S-4800，Hitachi，Japan）观察试片在不同放大倍率下的微观形貌。
参考图6，其是双相磷酸钙多孔陶瓷的孔径分布。通过图像分析方法，以平均直径表示经本发明制备的多孔陶瓷颗粒的孔径分布，本发明制备的多孔陶瓷颗粒有超过60%的孔洞的平均孔径大于100 μm。
参考图7，其是双相磷酸钙多孔陶瓷浸泡在模拟体液的pH变化图。模拟人体环境，本发明制备的多孔陶瓷颗粒在80小时后的pH变化趋向稳定，表示降解和沉积达到平衡。
模拟体液的离子浓度几乎等于血浆的离子浓度。模拟体液是通过试剂级NaCl（8.035 g/L）、NaHCO3（0.355 g/L）、KCl（0.225 g/L）、K2HPO4·3H2O（0.231 g/L）、MgCl2·6H2O（0.311 g/L）、CaCl2（0.292 g/L）和Na2SO4（0.072 g/L）的蒸馏水所制备。所述溶液在36.5±1℃下用三(羟甲基)氨基甲烷tris(hydroxylmethyl)aminomethane((CH2OH)3CNH2)和1 M盐酸（HCl）缓冲至pH 7.4。
参考图8，其是双相磷酸钙多孔陶瓷浸泡在SBF中7天后的FESEM照片，本发明制备的多孔陶瓷颗粒在浸泡在模拟体液7天后，表面有磷灰石沉积，可作为骨组织形成键结的用途，本发明制备的材料具有生物活性。
参考图9，其是细胞活性试验（3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, MTT）结果图，用以评估细胞毒性。
根据ISO10993-5进行的细胞毒性测试，样品试片以萃取的方式来评估细胞毒性。根据规范以0.2 g/mL的比例将样品（H、H/B、商用骨粉）浸泡在培养基中24小时萃取。稀释成不同比例（100、50、25、12.5%）与L929纤维母细胞在37℃下培养1天。
该试验中的样品为H、H/B、商用骨粉，其中H样品为水溶解牡蛎壳，经沉淀法反应30min合成的羟基磷灰石，经过发泡及1300℃烧结20 min后，得到的单相多孔羟基磷灰石颗粒；H/B样品为醋酸溶解牡蛎壳，经沉淀法反应12小时合成的羟基磷灰石，经过发泡及1000℃烧结25小时后，得到的双相多孔磷灰石颗粒（羟基磷灰石/β-三钙磷酸盐）；阳性对照组为苯酚；阴性对照组为三氧化二铝。
以0.2 g/mL的比例将样品（H、H/B、商用骨粉）浸泡在培养基中24小时进行萃取，并稀释成100%、50%、25%、12.5%的比例，与L929纤维母细胞在37℃下培养1天。
本发明制备的双相磷酸钙多孔陶瓷的细胞毒性试验结果显示，除了未稀释的样品，其余稀释50%、25%、12.5%比例都没有细胞毒性。
参考图10，其是第1、7、14天小鼠前驱干细胞的WST-8细胞活性试验。
试验组材料以25%培养基萃取24小时后，相当于50 mg/mL浓度，与D1细胞培养1、7、14天，并以WST试剂培养2小时后测量450 nm的吸光度，吸光度越高表示细胞数量越多、活性越强。
本发明制备的双相磷酸钙多孔陶瓷对小鼠前驱干细胞的细胞活性，在第14天优于商用套组。
参考图11，其是第1、7、14天D1小鼠前驱干细胞的碱性磷酸酶荧光活性（AlkalinePhosphatase Assay Kit, ALP）的骨分化试验，碱性磷酸酶活性可以用来判断成骨细胞的分化能力。
本发明制备的双相磷酸钙多孔陶瓷对小鼠前驱干细胞骨分化活性，在第7天优于商用套组。

Claims (9)

1.一种从含钙生物废弃物制备双相磷酸钙多孔陶瓷的两阶段烧结方法，其包含:
混合转动步骤，将羟基磷灰石和起泡剂混合成混合体，将所述混合体高速搅拌成泡沫状；
烘干步骤，将泡沫状混合体烘干成定型混合体；
第一阶段烧结步骤，将所述定型混合体在300度至900度下加热1至5小时；以及
第二阶段烧结步骤，将经过第一阶段烧结的定型混合体在900度至1400度下加热0.1至30小时，得到含有双相磷酸钙多孔陶瓷的骨填充材料。
2.根据权利要求1所述的方法，其中所述含钙生物废弃物为蛋壳、甲壳亚门动物的螃蟹壳、虾壳、龙虾壳、淡水龙虾壳与磷虾壳、双壳纲动物的牡蛎壳、蛤蛎壳、文蛤壳、贻贝壳、腹足纲动物的鲍鱼壳。
3.根据权利要求1所述的方法，其中所述混合转动步骤的起泡剂为椰子油起泡剂、葡萄糖起泡剂、氨基酸起泡剂、弱酸性起泡剂、月桂酰肌氨酸钠、月桂基甜菜碱、脂肪醇表面活性剂或其组合。
4.根据权利要求1所述的方法，其中所述混合转动步骤中所述羟基磷灰石和所述起泡剂的混合比例为10%比90%至90%比10%。
5.根据权利要求1所述的方法，其中所述混合转动步骤中高速转速为250至3000 rpm。
6.根据权利要求1所述的方法，其中所述烘干步骤中烘干温度为50至200度。
7.一种根据权利要求1至6中任一项所述的方法制成的双相磷酸钙多孔陶瓷，其包含:羟基磷灰石及β-三钙磷酸盐，其中所述羟基磷灰石体积百分比为20%至80%，所述β-三钙磷酸盐体积百分比为20%至80%。
8.根据权利要求7所述的双相磷酸钙多孔陶瓷，其中所述双相磷酸钙多孔陶瓷的孔洞尺寸介于50 μm至700 μm。
9.一种根据权利要求1至6中任一项所述的方法制成的双相磷酸钙多孔陶瓷的用途，其可用于骨填充、牙填充材料。
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