CN111320470A - 微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法 - Google Patents

微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法 Download PDF

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CN111320470A
CN111320470A CN202010070031.XA CN202010070031A CN111320470A CN 111320470 A CN111320470 A CN 111320470A CN 202010070031 A CN202010070031 A CN 202010070031A CN 111320470 A CN111320470 A CN 111320470A
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hydroxyapatite
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王欣宇
陈正雄
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Wuhan University of Technology WUT
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Abstract

本发明涉及一种微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法。该方法首先将氯化钙水溶液通过超声喷雾的方法与磷酸氢二钠水溶液混合，然后将混合液转入微波反应釜中进行反应得到纳米级羟基磷灰石粉体，最后将粉体压制成坯体并微波烧结成型即可。采用本发明方法能够在短时间内快速、大规模的制备分散性好、结晶度高的羟基磷灰石粉体，在烧结过程中不仅降低了烧结温度缩短了烧结时间，而且有效地抑制了晶粒长大，制得的陶瓷强度更高性能更好。

Description

微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法
技术领域
本发明涉及无机非金属材料技术领域，具体涉及一种微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法。
背景技术
羟基磷灰石是一种优良的生物医用材料，其具有良好的生物相容性，是人体骨骼和牙齿的主要成分。20世纪70年代开始，人工合成的羟基磷灰石材料开始逐步应用到人体硬组织损伤修复领域，70年代末期羟基磷灰石作为齿根移植材料开始应用在牙科修复中，到了90年代研究者开始关注羟基磷灰石陶瓷的力学性能和骨诱导性。作为骨损伤修复材料，羟基磷灰石可以根据受损部位的严重程度和骨缺损部位的形状制作成各种形式的骨修复材料，如纳米颗粒、致密陶瓷、微球、多孔支架以及羟基磷灰石涂层等。
羟基磷灰石陶瓷具有优良的生物相容性和骨诱导性，可作为外科植入材料直接植入人体内，修复人体受损的髋关节和其他骨组织，但羟基磷灰石陶瓷的力学性能较差、抗弯强度不高，难以在承重的关节部位广泛使用。
华南理工大学的徐玉彬(徐玉彬.渗透和包覆改性制备高生物活性羟基磷灰石陶瓷及其性能研究[D].广州：华南理工大学，2018)通过渗透改性和包覆改性的方法，向羟基磷灰石陶瓷中掺入锌离子和硅离子，提高了羟基磷灰石陶瓷的活性和降解性能，同时由锌离子渗透的羟基磷灰石陶瓷的抗压强度得到了明显提升，但是这种羟基磷灰石陶瓷的烧结温度高达1250℃持续烧结为2h，不仅能耗更大而且晶粒容易发生异常长大。
发明内容
本发明的目的在于克服现有技术存在的上述缺陷，提供一种微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法，该方法包括以下步骤：分别配制磷酸氢二钠水溶液和氯化钙水溶液，利用超声喷雾法将氯化钙水溶液喷入磷酸氢二钠水溶液中实现混合，期间控制混合液的pH为碱性，混合完成后将反应液转移至微波反应釜中进行反应，固液分离得到羟基磷灰石粉体；将羟基磷灰石粉体压制成坯，再转入微波烧结炉中烧结，最终得到羟基磷灰石陶瓷。
进一步的，磷酸氢二钠水溶液、氯化钙水溶液的浓度分别为0.1-0.4mol/L、0.5-1.0mol/L，保持两者混合时Ca/P摩尔比为1.67。
进一步的，氯化钙水溶液的喷射速度为8-12mL/min，超声喷雾混合期间用浓度为5-15mol/L的氨水溶液调解溶液的pH为9.5-10.5。
进一步的，反应液在微波反应釜中的升温速率为10-15℃/min，反应温度为150-170℃，反应时间为30-50h。
进一步的，反应液在微波反应釜中反应完自然冷却至室温，接着静置20-40min并弃去上清液，所得固体用去离子水反复洗涤多次，直至上清液为中性，再用醇溶剂(无水乙醇)洗涤多次，最后冷冻干燥得到羟基磷灰石粉体。
更进一步的，所述羟基磷灰石粉体的粒径为50-80nm，纯度为95％以上。
进一步的，羟基磷灰石粉体首先置于模具中以8-12MPa的压力单向加压5-10min得到粗坯，然后以180-220MPa的压力冷等静压5-10min，最后打磨得到坯体。
进一步的，坯体转移至微波烧结炉后以15-20℃的升温速率从室温升至1100-1150℃，保温烧结20-30min即可。
与现有技术相比，本发明的有益效果主要体现在以下几个方面:(1)克服了水热法和溶胶凝胶法制备羟基磷灰石普遍存在的产量低、产品热稳定性不好、合成周期较长、对环境有不利影响等缺点，本发明所采用的微波水热法具有反应时间短、速度快、能够大规模制备等优点，并且合成的粉体分散性较好、结晶度更高，可以烧结成强度更高的羟基磷灰石陶瓷；(2)本发明所使用的微波水热法不仅方法简单，而且制得的羟基磷灰石陶瓷有很好的生物相容性，可用于骨骼修复和诱导骨再生，无细胞毒性，致密度较高；(3)本发明使用的微波烧结法可以实现羟基磷灰石粉末更低温度下的快速烧结，不仅可以降低烧结温度而且大幅度缩短了烧结时间，因此能够有效抑制晶粒长大，此外微波加热的能量更高、坯体受热更加均匀，最终使得陶瓷的强度大幅度提高。
附图说明
图1是本发明实施例1制得的羟基磷灰石陶瓷断面3k倍扫描电子显微镜(SEM)照片。
图2是本发明实施例1制得的羟基磷灰石陶瓷断面6k倍扫描电子显微镜(SEM)照片。
具体实施方式
为使本领域普通技术人员充分理解本发明技术方案和有益效果，以下结合具体实施例及附图进行进一步说明。
实施例1
分别将14.32g磷酸氢二钠、9.8g二水氯化钙溶于100mL纯水中，磁力搅拌20min左右直至样品完全溶解，得到磷酸氢二钠水溶液和氯化钙水溶液。利用超声喷雾法将制得的氯化钙水溶液缓慢喷入到磷酸氢二钠水溶液中，磁力搅拌器转速为5r/min，液体喷射速度为10mL/min。在超声喷雾过程中不断向反应溶液中滴加氨水，调节混合液pH使其保持在10左右。将混合好的反应液置于微波反应釜中进行反应，设定升温速率为10℃/min、反应温度为160℃，保温时间40min。反应完成后得到羟基磷灰石溶液，将其冷却至室温后静置30min，去掉上清液后将剩余羟基磷灰石溶液倒入到50mL离心管中，以10000r/min的转速离心8min。倒掉上清液后加入30mL去离子水并搅拌均匀使固体完全溶解，继续离心，重复上述操作4至5次后，直至用pH试纸测得上清液pH在7左右。继续向反应物中加入35mL无水乙醇，重复离心洗涤2～3次，向洗涤后的样品中加入少量水溶解后转移至冷冻干燥机中，冷冻干燥24小时得到羟基磷灰石粉体。
取2.6g羟基磷灰石粉体置于50mm×10mm的铬钢模具中进行单向加压(压力大小为10MPa，保压时间5min)，得到长条形羟基磷灰石生胚。制得的胚体再进行冷等静压(压力大小200MPa，保压时间5min)，并用砂纸打磨加工成4mm×5mm×40mm的测试条，最后放入微波烧结炉中烧结(升温速率为20℃/min，烧结温度为1100℃，保温时间为20min)。最后将陶瓷加工成3mm×4mm×35mm的标准测试条，测得其抗弯强度为92MPa，该数值远远高于采用常规方法制备所得羟基磷灰石陶瓷的60MPa左右。
此外还对本实施例制得的羟基磷灰石陶瓷进行了SEM测试，结果分别如图1-2所示。由图1-2可知，使用微波烧结法制备的羟基磷灰石陶瓷十分致密且孔隙少，正是由于这种独特的微观结构提高了羟基磷灰石的抗弯强度。
实施例2
分别将14.32g磷酸氢二钠、9.8g二水氯化钙溶于100mL纯水中，磁力搅拌20min左右直至样品完全溶解，得到磷酸氢二钠水溶液和氯化钙水溶液。利用超声喷雾法将制得的氯化钙水溶液缓慢喷入到磷酸氢二钠水溶液中，磁力搅拌器转速为5r/min，液体喷射速度为10mL/min。在超声喷雾过程中不断向反应溶液中滴加氨水，调节混合液pH使其保持在10左右。将混合好的反应液置于微波反应釜中进行反应，设定升温速率为10℃/min、反应温度为160℃，保温时间40min。反应完成后得到羟基磷灰石溶液，将其冷却至室温后静置30min，去掉上清液后将剩余羟基磷灰石溶液倒入到50mL离心管中，以10000r/min的转速离心8min。倒掉上清液后加入30mL去离子水并搅拌均匀使固体完全溶解，继续离心，重复上述操作4至5次后，直至用pH试纸测得上清液pH在7左右。继续向反应物中加入35mL无水乙醇，重复离心洗涤2～3次，向洗涤后的样品中加入少量水溶解后转移至冷冻干燥机中，冷冻干燥24小时得到羟基磷灰石粉体。
取2.6g羟基磷灰石粉体置于50mm×10mm的铬钢模具中进行单向加压(压力大小为10MPa，保压时间5min)，得到长条形羟基磷灰石生胚。制得的胚体再进行冷等静压(压力大小200MPa，保压时间5min)，并用砂纸打磨加工成4mm×5mm×40mm的测试条，最后放入微波烧结炉中烧结(升温速率为20℃/min，烧结温度为1150℃，保温时间为35min)。最后将陶瓷加工成3mm×4mm×35mm的标准测试条，测得其抗弯强度为84MPa。
实施例3
分别将14.32g磷酸氢二钠、9.8g二水氯化钙溶于100mL纯水中，磁力搅拌20min左右直至样品完全溶解，得到磷酸氢二钠水溶液和氯化钙水溶液。利用超声喷雾法将制得的氯化钙水溶液缓慢喷入到磷酸氢二钠水溶液中，磁力搅拌器转速为5r/min，液体喷射速度为10mL/min。在超声喷雾过程中不断向反应溶液中滴加氨水，调节混合液pH使其保持在10左右。将混合好的反应液置于微波反应釜中进行反应，设定升温速率为10℃/min、反应温度为160℃，保温时间40min。反应完成后得到羟基磷灰石溶液，将其冷却至室温后静置30min，去掉上清液后将剩余羟基磷灰石溶液倒入到50mL离心管中，以10000r/min的转速离心8min。倒掉上清液后加入30mL去离子水并搅拌均匀使固体完全溶解，继续离心，重复上述操作4至5次后，直至用pH试纸测得上清液pH在7左右。继续向反应物中加入35mL无水乙醇，重复离心洗涤2～3次，向洗涤后的样品中加入少量水溶解后转移至冷冻干燥机中，冷冻干燥24小时得到羟基磷灰石粉体。
取2.6g羟基磷灰石粉体置于50mm×10mm的铬钢模具中进行单向加压(压力大小为10MPa，保压时间5min)，得到长条形羟基磷灰石生胚。制得的胚体再进行冷等静压(压力大小200MPa，保压时间5min)，并用砂纸打磨加工成4mm×5mm×40mm的测试条，最后放入微波烧结炉中烧结(升温速率为20℃/min，烧结温度为1100℃，保温时间为35min)。最后将陶瓷加工成3mm×4mm×35mm的标准测试条，测得其抗弯强度为73MPa。
实施例4
分别将14.32g磷酸氢二钠、9.8g二水氯化钙溶于100mL纯水中，磁力搅拌20min左右直至样品完全溶解，得到磷酸氢二钠水溶液和氯化钙水溶液。利用超声喷雾法将制得的氯化钙水溶液缓慢喷入到磷酸氢二钠水溶液中，磁力搅拌器转速为5r/min，液体喷射速度为10mL/min。在超声喷雾过程中不断向反应溶液中滴加氨水，调节混合液pH使其保持在10左右。将混合好的反应液置于微波反应釜中进行反应，设定升温速率为10℃/min、反应温度为160℃，保温时间40min。反应完成后得到羟基磷灰石溶液，将其冷却至室温后静置30min，去掉上清液后将剩余羟基磷灰石溶液倒入到50mL离心管中，以10000r/min的转速离心8min。倒掉上清液后加入30mL去离子水并搅拌均匀使固体完全溶解，继续离心，重复上述操作4至5次后，直至用pH试纸测得上清液pH在7左右。继续向反应物中加入35mL无水乙醇，重复离心洗涤2～3次，向洗涤后的样品中加入少量水溶解后转移至冷冻干燥机中，冷冻干燥24小时得到羟基磷灰石粉体。
取2.6g羟基磷灰石粉体置于50mm×10mm的铬钢模具中进行单向加压(压力大小为10MPa，保压时间5min)，得到长条形羟基磷灰石生胚。制得的胚体再进行冷等静压(压力大小200MPa，保压时间5min)，并用砂纸打磨加工成4mm×5mm×40mm的测试条，最后放入微波烧结炉中烧结(升温速率为15℃/min，烧结温度为1100℃，保温时间为35min)。最后将陶瓷加工成3mm×4mm×35mm的标准测试条，测得其抗弯强度为87MPa。

Claims (8)

1.微波水热法、微波烧结法联合制备羟基磷灰石陶瓷的方法，其特征在于该方法包括以下步骤：分别配制磷酸氢二钠水溶液和氯化钙水溶液，利用超声喷雾法将氯化钙水溶液缓慢喷入磷酸氢二钠水溶液中，期间控制混合液的pH为碱性，混合完成后将反应液转移至微波反应釜中进行反应，固液分离得到羟基磷灰石粉体；将羟基磷灰石粉体压制成坯，再转入微波烧结炉中烧结，最终得到羟基磷灰石陶瓷。
2.如权利要求1所述的方法，其特征在于：磷酸氢二钠水溶液、氯化钙水溶液的浓度分别为0.1-0.4mol/L、0.5-1.0mol/L，两者混合时保持Ca/P摩尔比为1.67。
3.如权利要求1所述的方法，其特征在于：氯化钙水溶液的喷射速度为8-12mL/min，超声喷雾混合期间用浓度为5-15mol/L的氨水溶液调解溶液的pH为9.5-10.5。
4.如权利要求1所述的方法，其特征在于：反应液在微波反应釜中的升温速率为10-15℃/min，反应温度为150-170℃，反应时间为30-50h。
5.如权利要求1所述的方法，其特征在于：反应液在微波反应釜中反应完自然冷却至室温，接着静置20-40min并弃去上清液，所得固体用去离子水反复洗涤多次，直至上清液为中性，再用醇溶剂洗涤多次，最后冷冻干燥得到羟基磷灰石粉体。
6.如权利要求1或5所述的方法，其特征在于：所述羟基磷灰石粉体的粒径为50-80nm，纯度为95％以上。
7.如权利要求1所述的方法，其特征在于：羟基磷灰石粉体首先置于模具中以8-12MPa的压力单向加压5-10min得到粗坯，然后以180-220MPa的压力冷等静压5-10min，最后打磨得到坯体。
8.如权利要求1所述的方法，其特征在于：坯体转移至微波烧结炉后以15-20℃的升温速率从室温升至1100-1150℃，保温烧结20-30min即可。
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