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金属学报  2017, Vol. 53 Issue (2): 140-152    DOI: 10.11900/0412.1961.2016.00163
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1 江苏科技大学材料科学与工程学院 镇江 212003
2 南京航空航天大学材料科学与技术学院 南京 210016
Analysis of Toughness and Strengthening Mechanisms forNi-CeO2 Nanocomposites Coated on the ActivatedSurface of Ti Substrate
Xiaowei ZHOU1(),Chun OUYANG1,Yanxin QIAO1,Yifu SHEN2
1 College of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
2 College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
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基于双脉冲电沉积技术在活性钛基(TA2)表面制备纳米晶Ni镀层。通过涂层附着力测试对比研究HF体系和DMF改良型活化液对TA2基体与表面镀层界面结合力的影响;借助TEM、FESEM和XRD等表征技术探讨添加纳米CeO2粒子前后对纳米电沉积层中Ni晶织构生长的影响;通过对纳米压痕及不同载荷下“十字交叉”型环形硬度压痕特征观察,分析复合CeO2粒子对Ni镀层表面强韧性的影响机制; 进一步探讨在高速干摩擦条件下复合CeO2粒子对Ni镀层抗磨损的作用。结果表明:在45+80 kHz交变频率超声振荡条件下,电解液中的活性CeO2粒子能有效吸附在优先生长Ni晶尖端,同时降低了Ni晶生长Gibbs自由能,并演变为Ni晶的催化形核中心来诱发异质形核; 纳米压痕测试表明:在500 g高载荷测试条件下,相对于纯Ni镀层试样的硬度压痕边缘的明显开裂和外拓迹象,Ni-CeO2复合镀层试样则表现为收敛性和连续完整的压痕边缘特征,显示出良好的强韧性。基于干摩擦过程中释放出大量的热,促使部分稀土CeO2相弥散或少量析出Ce溶质原子,具有对滑移的位错和晶界等缺陷产生钉扎拖拽作用,由此建立以Orowan位错绕过强化和位错塞积的机制模型;干摩擦过程促使部分富Ce磨损产物与NiO氧化膜机械混合来充当固体润滑剂,能起到良好的减摩作用,弥补了Ti表面耐磨性差等缺陷。

关键词 活性钛电沉积Ni-CeO2镀层组织性能富Ce润滑剂    

With industrial developments of aerospace vehicles, marine devices, biomedical and bones, pure Ti and its alloys have gained a great deal of attraction due to their superior properties. Despite having promising properties, limitations of lower hardness, inferior weldability, and poor brittle fracture have restricted their applications. So the objective of this work was to make surface electrodeposition of nanocrystalline Ni coatings on the surface of TA2 substrate using pulsed electrodeposition. Scratch tests was used to compare how effects of two typical HF and DMF activating solutions on modifying interfacial adhesion between TA2 substrate and surface coatings. In order to disclose crystal growth of Ni coating without and with CeO2 addition, a variety of characterizations such as FESEM, TEM and XRD were employed. A novel decussating-type microhardness with different loading forces attached with nanoindentation tests was conducted to make a comparative study of toughness and strengthening mechanisms between surface coatings and the un-coated TA2 substrate. Besides, wear behaviors of specimens was carried out using the ball-disc dry sliding tests. Results indicated that the addition of CeO2 nanoparticles into electroplating solution has effectively modified textural growth of Ni grains. This result was attributed to the presence of nano-sized CeO2 particles that adsorbed onto the preferred locations of crystal Ni growth, leading into an increasing catalytic site of nucleation to reduce Gibbs energy for grain refinement. According to observations of edges for hardness indentations, a smaller size with convergence feature for Ni-CeO2 coatings was indicative of effects of CeO2 nanoparticles or its precipiated Ce solute atoms on alloying-dispersion strengthening for completing defective grain boundaries. While for the case of a divergency state of indentations edges within obviously spalling cracks, it exhibited poor surface toughness for pure nickel. Furthermore, An analytic modeling validated here was based on the by-passing Orowan for dislocations pile-up mechanisms, in which this was contributed to the co-existence of Ce-rich worn products and NiO passive film to be expected as solid lubricants and make the self-lubricating effect, thereby improving wear resistance of Ti alloys where subjected to harsh conditions.

Key wordsactive titanium    electroplating    Ni-CeO2 coating    structural property    Ce-rich lubricating phase
收稿日期: 2016-04-29     
基金资助:国家自然科学基金项目No.51605203, 江苏省自然科学基金项目No.BK20150467和江苏科技大学博士科研启动金项目No.1062921501


周小卫,欧阳春,乔岩欣,沈以赴. 活性Ti表面电沉积Ni-CeO2复合镀层及其强韧性机理分析[J]. 金属学报, 2017, 53(2): 140-152.
Xiaowei ZHOU, Chun OUYANG, Yanxin QIAO, Yifu SHEN. Analysis of Toughness and Strengthening Mechanisms forNi-CeO2 Nanocomposites Coated on the ActivatedSurface of Ti Substrate. Acta Metall Sin, 2017, 53(2): 140-152.

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图1  在活化过程中TA2试样电位与浸泡时间之间的变化曲线
图2  TA2基体与Ni镀层结合界面的e-OM像
图3  添加CeO2纳米颗粒前后Ni 镀层表面的FESEM像
图4  添加CeO2纳米颗粒前后纳米晶Ni镀层中的晶界FESEM像
图5  添加纳米CeO2颗粒前后试样的XRD谱
图6  各试样纳米压痕的载荷-位移曲线
图7  不同载荷加载后残留在试样表面的硬度压痕的FESEM像
图8  各试样在500 g载荷作用下经“十字交叉法”环形加载后的硬度压痕的FESEM像
图9  各试样及其对应磨球的磨痕的FESEM像
图10  干摩擦前后纳米晶Ni-CeO2复合镀层的表面FESEM像
图11  干摩擦前后纳米晶Ni-CeO2复合镀层内部的TEM像
图12  富Ce固溶体相对晶界缺陷黏性钉扎的机理示意图
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