CN112174657A - 一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用 - Google Patents

一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用 Download PDF

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CN112174657A
CN112174657A CN202011055585.9A CN202011055585A CN112174657A CN 112174657 A CN112174657 A CN 112174657A CN 202011055585 A CN202011055585 A CN 202011055585A CN 112174657 A CN112174657 A CN 112174657A
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hydroxyapatite
ceramic slurry
photocuring
ceramic
powder
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刘耀
江泽星
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Jiangxi Jinshi 3d Intelligent Manufacturing Technology Co ltd
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Abstract

本发明提供了一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用，属于功能陶瓷领域。本发明提供的羟基磷灰石陶瓷浆料由改性羟基磷灰石粉末、丙烯酸酯、稀释剂、光引发剂按照质量比31‑100：10‑60:10‑60:1‑6制得；所述改性羟基磷灰石粉末由羟基磷灰石粉末、表面改性剂、分散剂按照质量比为30‑80:1‑10:1‑10制得。本发明还提供了一种通过真空搅拌，制备出了光固化的羟基磷灰石陶瓷浆料的方法，本发明还提供了一种将所述陶瓷浆料应用于多孔梯度结构的陶瓷支架的制备中。本发明提供的光固化羟基磷石灰浆料性能稳定，均匀性和分散性好。采用本发明的方法制备的羟基磷石灰多孔梯度陶瓷零件力学性能稳定，且制备方法简单，耗时短，成本低。

Description

一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用
技术领域
本发明涉及功能陶瓷技术领域，尤其涉及一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用。
背景技术
羟基磷石灰不但与人体骨骼晶体成分和结构基本一致，而且其生物的相容性、界面生物活性均由于医用钛、硅橡胶及植骨用碳材料等植入医用材料，另外有极好骨传导性和骨结合的能力，无毒副作用，所以被广泛用作硬组织修复材料和骨填充材料的生理支架以及疾病、意外事故中的骨修复材料。
传统的干压、注射成形尽管部分成型技术已经制备出羟基磷石灰陶瓷，但过度依赖于模具，难以满足高精度、高性能复杂结构致密羟基磷石灰陶瓷零件的制备要求。目前，采用固体无模成形技术(增材制造)制备结构复杂和高性能的陶瓷部件已成为研究热点。
光固化成形技术是将光敏树脂和陶瓷粉末混合而成的浆料，利用紫外线光束照射使其发生聚合反应形成固化坯体。目前，光固化已经成功地制备出复杂、致密的氧化物陶瓷。对于制备复杂、致密、表面精度高的陶瓷零件，光固化相比其它的增材制造技术具有不可比拟的优势，已经应用于医学与生物领域(如牙齿和骨骼修复)、微技术领域(如传感器、压电元件及光子晶体)及机械耐热结构领域等。
然而，目前针对多孔梯度的陶瓷，光固化成形技术的报道相对较少。尤其是缺乏多孔梯度的羟基磷石灰系统的研究，制约了羟基磷石灰在骨科医疗上的进一步的应用。
本发明通过成份的调控，成形出了复杂、结构的多孔梯度的羟基磷石灰陶瓷，使其能够更好地应用于医疗等领域。
发明内容
有鉴于此，本发明的目的在于提供一种光固化羟基磷石灰陶瓷浆料及其制备方法与应用，本发明提供的光固化羟基磷石灰陶瓷浆料性能稳定，在光固化成型时，成型过程稳定，得到的羟基磷石灰陶瓷性能稳定。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种光固化羟基磷石灰陶瓷浆料，由改性羟基磷灰石粉末、丙烯酸酯、稀释剂、光引发剂按照质量比31-100：10-60:10-60:1-6混合制得；所述改性羟基磷灰石粉末由羟基磷灰石粉末、表面改性剂、分散剂按照质量比为30-80:1-10:1-10混合制得。。
优选地，所述羟基磷石灰粉末的粒径为100-800nm在本发明中，所述羟基磷石灰粉末的粒径优选为100-800nm，更优选为400-600nm。本发明对所述羟基磷石灰粉末的来源没有任何特殊的限定，采用本领域技术人员熟知的市售商品即可。
优选地，所述表面改性剂包括KH550。
优选地，丙烯酸酯包括环氧丙烯酸酯(EA)、水性聚氨酯丙烯酸酯(PUA)、改性丙烯酸酯(WUV)中的一种或者几种任意比例的混合。
优选地，稀释剂为1，6-已二醇双丙烯酸酯(HDDA)和丙烯酸羟乙酯(HEA)中的一种或者几种任意比例的混合。
优选地，所述光引发剂为苯基双氧化磷(819)和1-羟基环已基苯基甲酮(184)中的一种或者几种任意比例的混合。在本发明中，所述光引发剂在紫外光的照射下，被激发产生自由基或阳离子等活性反应位点，引发预聚体和活性稀释剂发生交联反应。
本发明还提供了上述技术方案所述光固化羟基磷石灰陶瓷浆料的制备方法，包括以下步骤：
(1)将丙烯酸酯、稀释剂和光引发剂按照质量比10-80:10-60:1-10的比例进行搅拌球磨，得到树脂体系；
(2)将羟基磷石灰粉末、表面改性剂与分散剂按照30-80:1-10:1-10的比例进行搅拌球磨；其次再进行干燥，最终得到分散好的羟基磷石灰粉体；
(3)将所述步骤(2)得到的羟基磷石灰陶瓷粉末与所述步骤(1)得到的树脂体系混合，得到光固化羟基磷石灰陶瓷浆料；
对所述步骤(1)和(2)没有顺序限定。
本发明将羟基磷石灰粉末、表面改性剂和分散剂依次经混合和干燥，得到羟基磷石灰陶瓷粉末。本发明对所述混合的方式没有特殊的限定，采用本领域技术人员熟知的混合方式即可，具体的，如搅拌。搅拌速率为350-450r/min.所述搅拌的时间优选为5～20min，更优选为8～15min，最优选为10～12min。在本发明中，所述混合能够使羟基磷石灰陶瓷粉体和分散剂充分混合。
在本发明中，所述干燥的温度优选为30～80℃，更优选为40～70℃，最优选为50～60℃。在本发明中，所述干燥的时间优选为24～48h，更优选为30～40h，最优选为34～36h。
本发明将丙烯酸酯、活性稀释剂和光引发剂混合，得到树脂体系。本发明对所述混合的方式没有特殊的限定，采用本领域技术人员熟知的混合方式即可，具体的，如搅拌。在本发明中，所述搅拌的速率优选为350～450r/min，更优选为375～425r/min，最优选为400r/min。在本发明中，所述搅拌的时间优选为15～60min，更优选为20～50min，最优选为30～40min。
得到羟基磷石灰陶瓷粉末和树脂体系后，本发明将所述羟基磷石灰粉末与树脂体系混合，得到光固化羟基磷石灰陶瓷浆料。本发明对所述混合的方式没有特殊的限定，采用本领域技术人员熟知混合方式即可，具体的，如搅拌。在本发明中，所述搅拌的速率优选为350～450r/min，更优选为375～425r/min，最优选为400r/min。在本发明中，所述搅拌的时间优选为30～60min，更优选为35～55min，最优选为40～50min。
本发明还提供了上述技术方案中所述的光固化陶瓷浆料在制备羟基磷灰石的多孔梯度陶瓷支架的应用。
优选地，所述应用包括以下步骤：
(1)将光固化羟基磷石灰陶瓷浆料进行光固化，形成多孔结构的陶瓷支架；
(2)对所述步骤(1)得到的坯体依次进行脱脂和烧结，得到多孔梯度陶瓷结构的支架。
本发明将光固化羟基磷石灰陶瓷浆料进行光固化，形成坯体。在本发明中，所述光固化用光源的波长优选为365～450nm，更优选为380～420nm，最优选为390～410nm。本发明对所述光固化羟基磷石灰浆料的光固化次数没有限定，本领域技术人员根据需要进行调整即可。在本发明中，每次光固化的时间优选4～10s，更优选5～9s，更优选6～8s。在本发明中，每次光固化后光固化产物的厚度优选为0.02～0.05mm，更优选0.03～0.04mm，最优选0.035mm。本发明优选对光固化羟基磷石灰陶瓷浆料进行多次固化，提高光固化浆料的光固化效果，而且也能够制备出形状较复杂的坯体。
在本发明中，所述光固化优选在光固化设备中，按照预先设计的图形，得到坯体。本发明对图形没有特殊的限定，本领域技术人员根据需要进行设计即可。
得到坯体后，本发明将坯体依次进行脱脂和烧结，得到羟基磷石灰陶瓷零件。在本发明中，所述脱脂的温度优选为500～800℃，更优选600～700℃，最优选650～700℃，脱脂的时间为60-120min，更优选为60-90min，最优选为80min。本发明中，所述升温至脱脂温度的升温速率优选为0.5～2℃/min，更优选为0.8～1.6℃/min，最优选为1.0～1.4℃/min。在本发明中，所述脱脂能够脱除坯体中的活性稀释剂。
在本发明中，所述烧结的压力优选为0.2～0.5MPa，更优选为0.3～0.4MPa，最优选为0.35MPa。在本发明中，所述烧结的温度优选为1100～1250℃，更优选为1150～1250℃，最优选为1200～1250℃，所述烧结的时间优选为48-96h，更优选为72-96h，最优选为80h。本发明中，所述烧结能够使羟基磷石灰多孔梯度零件。
本发明的有益效果：
本发明提供的光固化羟基磷石灰浆料性能稳定，均匀性和分散性好。采用本发明的方法制备的羟基磷石灰多孔梯度陶瓷零件力学性能稳定，且制备方法简单，耗时短，成本低。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
实施例1-3和对比例1-3
一种光固化羟基磷石灰浆料包括以下重量份数的组分：改性羟基磷石灰粉末，稀释剂，光引发剂。
所述改性羟基磷石灰粉末由羟基磷石灰粉末、表面改性剂和分散剂混合而成。
在实施例和对比例中，各组分的用量以羟基磷石灰粉末为基准，按照质量比计算。
改性羟基磷石灰粉末的配方如表1所示：
表1
Figure BDA0002710778810000051
光固化羟基磷石灰陶瓷浆料的配方如表2所示：
表2
Figure BDA0002710778810000052
Figure BDA0002710778810000061
光固化羟基磷石灰浆料的制备方法，包括以下步骤：
(1)将羟基磷石灰粉末、分散剂、表面改性剂混合后干燥，得到改性羟基磷石灰粉末；
(2)将丙烯酸酯、活性稀释剂和光引发剂混合，得到树脂体系；
(3)将所述步骤(1)得到的改性羟基磷石灰粉末与所述步骤(2)得到的树脂体系混合，得到光固化羟基磷石灰浆料。
各步骤参数见表3所示。
表3
Figure BDA0002710778810000062
Figure BDA0002710778810000071
光固化羟基磷石灰浆料在制备羟基磷石灰陶瓷的应用，包括以下步骤；
(1)将光固化羟基磷石灰料进行光固化，形成坯体；
(2)对得到的坯体依次进行脱脂和烧结，得到羟基磷石灰陶瓷零件。
其中，光固化、脱脂、烧结的具体参数见表4所示。
表4
Figure BDA0002710778810000081
采用力学性能测试标准，测试上述实施例和对比例制备的羟基磷石灰陶瓷，羟基磷石灰陶瓷具有很好的力学性能。测试结果如表5所示。
表5
Figure BDA0002710778810000082
Figure BDA0002710778810000091
最后需要强调的是，以上所述仅为本发明的优选实施例，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种变化和更改，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种光固化羟基磷灰石陶瓷浆料，其特征在于，由改性羟基磷灰石粉末、丙烯酸酯、稀释剂、光引发剂按照质量比31-100：10-60:10-60:1-6制得；所述改性羟基磷灰石粉末由羟基磷灰石粉末、表面改性剂、分散剂按照质量比为30-80:1-10:1-10制得。
2.根据权利要求1所述的光固化羟基磷灰石陶瓷浆料，其特征在于，所述羟基磷灰石粉末的粒径为100-800nm；所述表面改性剂包括KH550。
3.根据权利要求1所述的光固化羟基磷灰石陶瓷浆料，其特征在于，所述的丙烯酸酯包括环氧丙烯酸酯(EA)、水性聚氨酯丙烯酸酯(PUA)、改性丙烯酸酯(WUV)中的任意一种或者几种的混合。
4.根据权利要求1所述的光固化羟基磷灰石陶瓷浆料，其特征在于，所述稀释剂为1，6-已二醇双丙烯酸酯(HDDA)、丙烯酸羟乙酯(HEA)、三羟甲基丙烷三丙烯酸酯(TMPTA)中的任意一种或者几种的混合。
5.根据权利要求1所述的光固化羟基磷灰石陶瓷浆料，其特征在于，所述光引发剂为苯基双氧化磷和1-羟基环已基苯基甲酮中的任意一种或者几种的混合。
6.权利要求1-5任一项所述的光固化羟基磷灰石陶瓷浆料的制备方法，包括以下步骤：
(1)将丙烯酸酯、稀释剂和光引发剂按照质量比10-60:10-60:11-10的比例进行搅拌球磨，得到树脂体系；
(2)将羟基磷石灰粉末、表面改性剂与分散剂按照30-80:1-10:1-10的比例进行搅拌球磨，其次再进行干燥，最终得到分散好的改性羟基磷酸三钙粉体。
(3)将所述步骤(2)得到的羟基磷石灰粉末与所述步骤(1)得到的树脂体系混合，得到光固化羟基磷石灰陶瓷浆料。
7.权利要求1～5任一项所述的光固化羟基磷石灰陶瓷浆料在制备羟基磷石灰多孔梯度陶瓷支架中的应用。
8.根据权利要求7所述的光固化羟基磷石灰陶瓷浆料在制备羟基磷石灰多孔梯度陶瓷支架中的应用，其特征在于，包括以下步骤：
(1)将光固化羟基磷石灰陶瓷浆料进行光固化，形成多孔结构的陶瓷支架；
(2)对所述步骤(1)得到的坯体依次进行脱脂和烧结，得到梯度的多孔结构的陶瓷支架零件。
9.根据权利要求7所述的光固化羟基磷石灰陶瓷浆料在制备羟基磷石灰多孔梯度陶瓷支架中的应用，其特征在于，所述步骤(1)中光固化用光源的波长为365～460nm。
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CN108424149A (zh) * 2018-04-27 2018-08-21 中南大学 光固化氮化硅陶瓷浆料
CN109650909A (zh) * 2019-02-20 2019-04-19 四川大学 一种基于光固化3d打印技术的磷酸钙骨诱导生物陶瓷支架及其制备方法
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CN108424149A (zh) * 2018-04-27 2018-08-21 中南大学 光固化氮化硅陶瓷浆料
CN109650909A (zh) * 2019-02-20 2019-04-19 四川大学 一种基于光固化3d打印技术的磷酸钙骨诱导生物陶瓷支架及其制备方法
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