CN108359826A - 一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法 - Google Patents
一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法 Download PDFInfo
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Abstract
本发明公开了一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法，属于生物植入材料领域。该方法是：选用单一相结构Ta2O5陶瓷粉末，在低氧浓度下(<100ppm)诱导激光烧结过程中形成的Ta2O5液相发生热力学还原反应Ta2O5→2Ta+5/2O2，通过Ta2O5自分解和氧气的逸出，降低Ta2O5液相中氧含量并使成分进入Ta‑O溶液的液相分离区，凝固后形成弥散分布的Ta2O5/Ta两相组织。本发明所制备的Ta2O5/Ta金属陶瓷兼具金属的强韧性和陶瓷材料的耐磨性能，其硬度和耐体液磨损性能与Ta金属相比提高5倍以上，特别适用于生物植入材料领域。
Description
技术领域
本发明属于生物植入材料领域，具体涉及一种基于还原反应激光选区烧结制备新型Ta2O5/Ta金属基复合陶瓷技术，该复合陶瓷可应用于对耐腐蚀耐磨损要求较高的人体植入材料。
背景技术
钽作为一种金属生物材料具有极强的耐腐蚀性和优异的生物相容性，在人体植入材料，特别是在骨关节替代方面展现了潜在的医疗应用前景。但是，钽金属约120HV左右较低的显微硬度使其抗磨损性能下降。最近，研究发现Ta2O5陶瓷与钽金属相比，具有更高的耐体液腐蚀磨损性能、优良的生物相容性，并且能够提供更加优异的骨生长和附着性能。中国专利公开号CN106757004A采用激光熔覆技术在常规大气环境下制备了单一相结构的Ta2O5陶瓷涂层，熔覆过程首先将Ta2O5陶瓷粉末预铺在钽金属表面，随后利用高功率激光烧结使Ta2O5陶瓷熔化并在钽基体表面凝固成涂层，再通过多层熔覆制成具有一定尺寸厚度和单一Ta2O5相结构的陶瓷层。但是，陶瓷相固有的高脆性特点使单一相结构的Ta2O5陶瓷涂层仍难以替代骨关节作为植入材料。
金属陶瓷因兼具金属基体和陶瓷增强相的优点，如前者的强韧性和抗弯性，后者的高硬度和结构稳定性等成为骨植入物材料重要的研究方向之一。一般而言，陶瓷增强相的添加主要有外加法和原位自生法。外加法存在分布不均，与增强相-基体界面处易形成裂纹等问题。而原位自生法增强相具有分布均匀、粒径细小、界面相容性更高等显著优点，是制造金属陶瓷植入物理想的工艺途径。本发明结合先进的激光选区烧结(3D打印)设备，提出了一种通过严格控制烧结环境中的氧分压，诱导激光烧结过程中形成的Ta2O5液相发生热力学还原反应，通过Ta2O5自分解和氧的逸出，激光选区烧结制备原位自生Ta2O5/Ta金属基复合陶瓷的3D原型制造技术。目前，有报道采用激光熔覆、磁控溅射和化学气相沉积等方法制备纯Ta2O5陶瓷涂层，但未见基于还原反应制备原位自生Ta2O5/Ta金属基陶瓷的研究报道。
发明内容
针对钽金属植入物硬度和耐磨损性能较低的缺陷，本发明要解决的技术问题是提供一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法，以期该方法制备的金属陶瓷兼具金属的强韧性和陶瓷材料的耐磨性能，能适用于生物植入材料领域。
为解决以上技术问题，本发明是通过以下技术方案予以实现的。
本发明提供了一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法，所述激光选区烧结环境要求的氧浓度临界值必须<100ppm；所述激光选区烧结选用的烧结粉末为具有单一相结构的Ta2O5陶瓷，纯度>99.5％。
所述烧结得到的Ta2O5/Ta金属陶瓷为具有原位自生的Ta2O5和Ta两相均匀结构。
上述方法制备的Ta2O5/Ta金属陶瓷可在对耐腐蚀耐磨损要求较高的人体植入材料中加以应用。
所述激光选区烧结制备技术既可是传统的激光熔覆技术制备涂层，也可与3D打印原型制造技术结合制备具有特定形状要求的骨或支架等植入物；制备过程即可是预置粉方法也可是送粉方法。
激光选区烧结预置粉方法为：第一步将Ta2O5陶瓷粉末预置于金属基板表面，铺粉厚度为0.8～1.5mm；第二步通过激光烧结使粉末在满足要求的氧分压环境下熔化，熔化的Ta2O5液相通过还原反应逸出氧气从而可降低Ta-O液相中氧浓度，再通过后续凝固过程中Ta-O混合液体的液相分离行为形成厚度约0.2～0.5mm的Ta2O5/Ta金属陶瓷两相复合涂层，完成一层熔覆或打印；第三步将基板下降一层粉末厚度的高度，在前一层熔覆层上再均匀铺上所述Ta2O5粉末进行激光烧结；最后，重复第一步至第三步，直至待成形零件加工成型，然后关闭激光扫描系统，待零件冷却至室温时取出。
激光选区烧结送粉方法为：利用先进的送粉装置将粉末连续直接输送入激光光斑内，随着光斑按照3D原型模型方式移动，通过粉末一层层的熔化凝固，最终成型的方式，整个制备过程也需在满足要求的氧分压环境下进行。
本发明的科学原理如下：
在激光高温热源作用下，Ta2O5陶瓷粉末熔融为液相，根据附图说明1中的Ta-O相图，若要获得Ta2O5和Ta两相原位自生复合结构，必须降低Ta2O5熔融液相中的氧含量，使得熔融液相可以进入液相分离区，即可形成富钽低氧区(L1)与富氧区(L2)。因此，本发明创造性的提出了在低氧浓度环境下激光选区烧结Ta2O5陶瓷粉末，利用液相Ta2O5的还原反应Ta2O5→2Ta+5/2O2，促进Ta-O液相中氧的逸出，从而制备原位自生Ta2O5-Ta两相复合材料。Ta2O5还原反应对环境氧临界分压的要求可根据范特霍夫方程方程进行计算，具体热力学计算如下：
上述公式中，式(1)为Ta2O5还原反应标准摩尔吉布斯自由能式(2)为Ta2O5还原反应的实际吉布斯自由能(ΔGT)同氧分压和反应温度之间的关系。由式(2)可知，当反应实际吉布斯自由能等于零时，还原反应达到临界点。标准摩尔吉布斯自由能与温度(T)的关系可由公式(3)得出：
根据以上公式，最终得出Ta2O5还原分解反应的临界氧分压与温度的计算关系如附图2所示。可见，当某烧结温度下环境中氧的浓度低于临界氧分压，则会诱导熔池中Ta2O5液相发生还原反应，促进Ta-O液相中氧的逸出，从而制备原位自生Ta2O5-Ta两相复合材料。一般而言，激光熔池温度至少会明显超过Ta2O5陶瓷相的1872℃熔点温度，而所需的临界氧分压随着熔池温度的升高会逐渐升高。因此，激光熔池温度越高，发生还原反应所要求的临界氧分压越高。
与现有技术相比，本发明具有以下技术效果：
1、以往激光熔覆技术在惰性气体保护或大气环境下进行的目的都是为了避免涂层金属氧化，保证涂层材料成分不发生变化。但是，在大气或对氧浓度不做具体要求的惰性气体保护下进行Ta2O5陶瓷粉末烧结，Ta2O5陶瓷熔化后由于成分没有明显改变，凝固后仍然为单一相结构的Ta2O5陶瓷，而陶瓷相固有的高脆性限制了Ta2O5陶瓷涂层的应用前景。本发明则结合Ta2O5高温液相在低于临界氧分压时会发生还原反应，通过严格控制烧结环境中的氧浓度，诱导Ta2O5还原分解和氧的逸出，激光选区烧结制备原位自生Ta2O5/Ta金属基复合陶瓷。这种通过严格控制烧结环境中氧浓度改变激光选区烧结材料成分和凝固相组织的控制措施以往未见报道，也未见以往有报道采用原位自生法制备高性能Ta2O5/Ta金属基陶瓷的研究。
2、与外加法将Ta2O5和Ta两种粉末进行机械混合后再进行激光选区烧结相比，本发明利用低氧浓度条件下Ta2O5液相还原反应制备原位自生Ta2O5/Ta金属陶瓷，陶瓷颗粒增强相具有分布更加均匀、尺寸细小、抗裂纹和韧性更好等显著优点，制备后Ta2O5/Ta金属基复合陶瓷的耐蚀性、硬度和耐体液腐蚀磨损性能均远高于钽金属，其硬度和耐体液磨损性能与Ta金属相比提高5倍以上，特别适用于生物植入材料领域。
附图说明
图1是钽-氧二元合金相图。
图2是计算所得Ta2O5还原反应临界氧分压与温度的关系曲线。
图3是实施例激光烧结Ta2O5/Ta金属陶瓷X射线衍射谱。
图4是实施例激光烧结Ta2O5/Ta金属陶瓷扫描电镜组织。
图5是实施例激光烧结Ta2O5/Ta金属陶瓷和纯Ta金属在Hank’s溶液中的腐蚀磨损的摩擦系数变化规律。
图6是实施例激光烧结Ta2O5/Ta金属陶瓷和纯Ta金属在Hank’s溶液中的腐蚀磨损后磨痕的扫描电镜形貌。
具体实施例
以下结合附图及具体实施例，对本发明作进一步说明，但本发明不局限于下述实施例。
从市场购买商业化Ta2O5陶瓷粉末做3D打印粉末材料，激光烧结设备为美国OptomecLENS(Laser Engineered Net Shaping)3D金属喷印激光成型机，型号为MR-7，最大功率1kW光纤激光器，波长1070nm。首先，将Ta2O5陶瓷粉末预铺在激光3D打印Ta基板上，厚度为0.8-1.5mm。然后，激光3D打印机在卧式圆柱体手套箱内对粉末进行激光打印，激光工艺参数为：激光功率0.6kW，扫描速度600mm/min。打印后第一层涂层厚度约0.2～0.5mm。再然后，重复上述步骤在第一层Ta2O5涂层表面依次打印第二、第三和第四层Ta2O5。整个烧结手套箱内充高纯氩气，手套箱内氧浓度控制在<100ppm。
图3和图4分别为低氧浓度环境下激光选区烧结Ta2O5陶瓷粉末凝固后X射线衍射图谱和扫描电镜组织照片，可以看出Ta2O5陶瓷粉末凝固后转变为Ta2O5和Ta两相结构。图4所示凝固组织有Ta2O5和Ta两相组成，EDS能谱分析显示黑色Ta2O5陶瓷弥散均匀分布在白色Ta金属基体上，组织均匀细小。其中，白色Ta基体中Ta和O摩尔百分含量分别为76.4％和23.6％，黑色Ta2O5相中Ta和O摩尔百分含量分别为23％和77％。表明低氧浓度条件下激光选区烧结起到了诱导Ta2O5发生还原反应，氧气逸出降低了熔融Ta-O液相中氧含量，液相成分进入图1中Ta-O相图L1+L2液相分离区，凝固后经液相分离形成了Ta2O5/Ta两相弥散均匀分布的金属陶瓷结构。
Ta2O5/Ta金属陶瓷显微硬度约518HV0.5，远高于纯钽金属约120HV的显微硬度。图5比较了Ta2O5/Ta金属陶瓷与纯钽金属在Hank’s人体模拟溶液腐蚀磨损过程中摩擦系数的变化规律，对磨材料为直径5.4mm的Al2O3球。可以看出纯Ta金属摩擦系数波动较大，变化范围在0.15～0.3之间。相反，Ta2O5/Ta金属陶瓷的摩擦系数在0.07～0.09较小范围内波动，表明Ta2O5/Ta金属陶瓷润滑性及耐腐蚀磨损性能明显高于钽金属。图6(a)和图6(b)分别是Ta2O5/Ta金属陶瓷与Ta金属磨损后的磨痕形貌，经计算Ta2O5/Ta金属陶瓷磨痕深度和宽度分别为0.08mm和0.3mm，纯钽腐蚀磨损后的磨痕深度和宽度分别为0.47mm和3.6mm，从深度判断Ta2O5/Ta金属陶瓷耐腐蚀磨损性能与纯钽相比提高5倍以上。
进一步，本发明为了充分证明本实验条件下熔池中Ta2O5液相发生了还原反应，涂层中的形成的Ta金属相并非从熔化的Ta基板上浮而来。采用相同制备条件下在氧化铝基体表面进行了激光选区烧结单一Ta2O5陶瓷粉末的实验，实验结果也获得了类似Ta2O5/Ta两相结构的金属陶瓷。表明Ta2O5陶瓷粉末在激光高温烧结熔池中确实发生了还原反应，被部分还原成金属钽。
Claims (3)
1.一种基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法，其特征在于，所述激光选区烧结环境要求的氧浓度临界值必须<100ppm；所述激光选区烧结选用的烧结粉末为具有单一相结构的Ta2O5陶瓷，纯度>99.5％。
2.如权利要求1所述的基于还原反应激光选区烧结原位自生Ta2O5/Ta金属陶瓷的方法，其特征在于，所述烧结得到的Ta2O5/Ta金属陶瓷为具有原位自生的Ta2O5和Ta两相均匀结构。
3.如权利要求1所述方法得到的Ta2O5/Ta金属陶瓷在对耐腐蚀耐磨损要求较高的人体植入材料中的应用。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777276A (zh) * | 2019-10-23 | 2020-02-11 | 广东工业大学 | 一种基于激光3d打印的氧化铝增强合金性能的方法 |
| CN113105250A (zh) * | 2021-04-15 | 2021-07-13 | 山东大学 | 用于增材制造的石榴状黑色陶瓷颗粒及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042620A1 (fr) * | 2009-10-08 | 2011-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Formation de particules métalliques sur un support solide à base d'oxyde et muni de deux fonctions chimiques distinctes greffées |
| RU2518257C1 (ru) * | 2012-11-27 | 2014-06-10 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Способ формирования покрытий пентаоксида тантала на подложке |
| CN104152840A (zh) * | 2014-08-06 | 2014-11-19 | 常州大学 | 一种制备具有特殊微纳结构TiO2/Ta2O5复合涂层的方法 |
| CN106757004A (zh) * | 2016-12-27 | 2017-05-31 | 安徽工业大学 | 一种钽金属表面激光多层熔覆Ta2O5陶瓷涂层的方法 |
-
2018
- 2018-02-12 CN CN201810145452.7A patent/CN108359826B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042620A1 (fr) * | 2009-10-08 | 2011-04-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Formation de particules métalliques sur un support solide à base d'oxyde et muni de deux fonctions chimiques distinctes greffées |
| RU2518257C1 (ru) * | 2012-11-27 | 2014-06-10 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Способ формирования покрытий пентаоксида тантала на подложке |
| CN104152840A (zh) * | 2014-08-06 | 2014-11-19 | 常州大学 | 一种制备具有特殊微纳结构TiO2/Ta2O5复合涂层的方法 |
| CN106757004A (zh) * | 2016-12-27 | 2017-05-31 | 安徽工业大学 | 一种钽金属表面激光多层熔覆Ta2O5陶瓷涂层的方法 |
Non-Patent Citations (1)
| Title |
|---|
| 张超: "选区激光熔化技术制备多孔钽工艺及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777276A (zh) * | 2019-10-23 | 2020-02-11 | 广东工业大学 | 一种基于激光3d打印的氧化铝增强合金性能的方法 |
| CN110777276B (zh) * | 2019-10-23 | 2021-05-28 | 广东工业大学 | 一种基于激光3d打印的氧化铝增强合金性能的方法 |
| CN113105250A (zh) * | 2021-04-15 | 2021-07-13 | 山东大学 | 用于增材制造的石榴状黑色陶瓷颗粒及其制备方法和应用 |
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