烧结型NdFeB永磁体表面功能性膜层的制备及性能研究
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摘要
第三代稀土钕铁硼(NdFeB)永磁体因其高的饱和磁通量、矫顽力、磁能积(BH)max、良好的机械加工特性和相对低廉的价格,在声学、航空、电子、自动化、生物和通讯等许多领域得到广泛应用。但NdFeB永磁体的耐腐蚀性能非常差,在腐蚀介质或潮湿环境中易形成腐蚀原电池,使磁体组成和结构发生变化,导致磁性能下降乃至最终粉化,严重阻碍和限制了其在众多领域的广泛应用。抗腐蚀性能已经成为评价NdFeB永磁体应用性能的关键指标,因此提高NdFeB永磁体在实际应用环境中的耐腐蚀性能具有十分重要的意义。
迄今为止所报道的关于烧结型NdFeB永磁体表面腐蚀保护膜层的研究主要侧重于工艺研究及其短期耐腐蚀性能测试,而对膜层在实际腐蚀环境中的腐蚀保护能力的长期跟踪测试、膜层电化学腐蚀行为变化、失效机理方面的探讨则鲜有报道。膜层对NdFeB磁体长期的腐蚀保护性能研究对于该磁体的广泛应用更具有指导意义。
基于以上问题,本文在研究和借鉴近年来国内外有关烧结型NdFeB永磁体及其它金属材料腐蚀研究方法的基础上,通过大量的正交试验,在烧结型NdFeB永磁体表面制备出多种具有优异耐腐蚀性能的膜层,并利用电化学极化、电化学阻抗谱和浸泡等测试跟踪膜层在实际腐蚀环境对永磁体的腐蚀保护能力的变化,分析和探讨了膜层的电化学腐蚀行为及失效机理。本论文通过电沉积和溶胶凝胶技术相结合的方法,首次制备了封孔的Ni-TiO2复合膜层、Ni-Co合金镀层、Ni-Co-TiO2合金复合镀层和硅烷处理的Zn-TiO2梯度膜层。本文的主要研究内容如下：
(1)以环境友好和操作工艺相对简易为前提,结合溶胶凝胶技术及脉冲电沉积技术,在烧结型NdFeB永磁体表面制备了密封的Ni-TiO2复合膜层(SCC)。作为对比,对未封孔的Ni-TiO2复合膜层(UCC)也做了相应研究。电化学阻抗和极化测试结果表明SCC具有比UCC更为优异的耐腐蚀性能,能够为烧结型NdFeB永磁体提供更好的腐蚀保护。为了更深入研究SCC对永磁体的实际保护性能,采用电化学阻抗谱技术测试及分析了SCC在中性3.5wt.%NaCl腐蚀介质长期浸泡过程中耐腐蚀性能的变化及失效机理。浸泡实验结果显示,SCC的电化学腐蚀行为分三个阶段。第一阶段是浸泡时间1 h到240 h,这一阶段观察到三个部分重叠的时间常数,此时SCC的阻抗模值|Z|仍然非常高,说明此阶段膜层可以对基体提供优异的腐蚀保护。第二阶段是浸泡时间240 h到264 h,该阶段观察到两个明显的时间常数,且SCC的阻抗模值|Z|急剧下降,但SCC仍然对基体提供了良好的保护。第三阶段是浸泡时间达到288 h,此阶段只观察到一个明显的时间常数,同时SCC的阻抗模值|Z|下降更多,表明SCC对基体的腐蚀保护作用已经消失。
(2)应用电沉积技术在烧结型NdFeB永磁体表面制备了耐腐蚀性能优异的Ni-Co合金镀层。采用扫描电子显微镜(SEM)、能量散射谱(EDS)、X射线衍射(XRD)、动电位极化曲线、电化学阻抗谱(EIS)和浸泡腐蚀等测试手段表征该合金镀层的微观结构、形貌及耐腐蚀性能。微观结构分析表明,Ni-Co合金镀层是溶质原子(Co原子)占据溶剂(Ni原子)晶格中的结点位置而形成的置换固溶体(fcc)；Ni基质金属中Co元素的添加,导致了Ni基质金属的择优取向从(200)晶面变为(111)晶面。表面形貌测试说明,由于Ni-Co合金镀层晶粒发生细化,所以具有比纯镍镀层更为致密的形貌；动电位测试结果显示,Ni-Co合金镀层具有比纯镍镀层更正的腐蚀电位(Econ),更小的腐蚀电流密度(icon)；EIS的长期浸泡实验结果表明该合金镀层在浸泡576 h后对基体仍具有良好的腐蚀保护能力,而纯镍镀层在浸泡144 h小时后,其腐蚀保护能力已经丧失。这进一步揭示了Ni-Co合金镀层比纯镍镀层有更好的耐腐蚀性能。
(3)为了进一步扩大烧结型NdFeB永磁体使用范围,本论文运用复合电沉积方法在烧结型NdFeB永磁材料表面制备了Ni-Co-TiO2复合镀层。通过EIS和电化学极化测试研究了该镀层在0.5 mol L-1 H2SO4, 0.6 mol L-1 NaOH,0.6 mol L-1 Na2SO4和中性的3.5wt.%NaCl腐蚀介质中的电化学腐蚀行为。实验结果表明,该复合镀层在多种腐蚀介质中对永磁体均具有良好的腐蚀保护性能。为了更深入研究该镀层的腐蚀保护能力及实用性,本文采用EIS研究了Ni-Co-TiO2合金复合镀层在中性3.5wt.%NaCl腐蚀介质长期浸泡过程中的电化学腐蚀行为变化及其原因。长期浸泡实验结果揭示了在3.5wt.%NaCl腐蚀环境中该复合镀层能够为烧结型NdFeB永磁体提供长期腐蚀保护的原因：Ni-Co-TiO2复合镀层表面生成了钝化膜。
(4)以环境友好、操作工艺相对简化和降低工艺成本为前提,结合溶胶凝胶技术和电沉积技术,在烧结型NdFeB永磁体表面制备了具有机械隔离和电化学保护的双重腐蚀保护作用的膜层,即阳极性Zn-TiO2硅溶胶梯度膜层(TZT)。利用电化学阻抗谱和极化测试研究了TZT在中性3.5wt.%NaCl腐蚀介质中的耐腐蚀性能。为了进一步研究TZT的耐腐蚀性能,在中性3.5wt.%NaCl腐蚀介质中进行了长期浸泡实验。对比Zn-TiO2镀层浸泡264 h及TZT浸泡336h后的表面腐蚀形貌发现,由于溶胶层对腐蚀介质的阻挡作用,使腐蚀介质的传输受到阻碍,TZT显示出更好的耐腐蚀性能,从而对烧结型NdFeB永磁体提供了更好的腐蚀保护。
The sintered NdFeB (neodymium-iron-boron) permanent magnet as the third-era permanent magnet, which exhibits excellent magnetic properties such as high remanence, high coercivity, large energy product, good machinability and comparatively low price, has been used for many applications in various fields such as acoustics, aviation, electronics, automation, biomedical and communications. However, the anticorrosive properties of sintered NdFeB permanent magnet are very poor, and easily form the galvanic corrosion in corrosive media and humid environment, which results in the changes in the composition and microstructure of magnet, and then the decline of the magnetism. This severely impedes and limits the extensive application of NdFeB magnet in various fields. The anticorrosive properties of NdFeB magnet have become a key index to estimate its application properties. Therefore, it is very important to improve the corrosion resistance of NdFeB permanent magnets.
So far, most of the researches on the corrosion protection of sintered NdFeB permanent magnet were emphasizing particularly on the investigation on technical study and tests of the short-term protective properties of coatings or films prepared on sintered NdFeB permanent magnet in corrosive media. Unfortunately, few works were focusing on the tests of the long-term anticorrosive properties and the changes in electrochemical corrosion behaviors in corrosive media, as well as the failure mechanism, which may be an indicator of the actual corrosion protection properties of coatings or films provided for sintered NdFeB permanent magnet.
Based on the problems mentioned above, different films or coatings possessed excellent anticorrosive properties were prepared by dint of large numbers of orthogonal experiments, which were on the basis of the investigation on the corrosion protection of sintered NdFeB permanent magnet and other metals. The potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) techniques and immersion tests were employed to study the changes in the actual corrosion protection properties of films or coatings provided for permanent magnet in service environment. Sealed Ni-TiO2 composite coating, Ni-Co alloy coating, Ni-Co-TiO2 composite coating and silicane treated Zn-TiO2 grade film were firstly prepared on sintered NdFeB permanent magnet by the combination of electrodeposition and sol-gel methods. The major research works in the present study are as follows:
(1) Taking into account environment friendly and simplifying operation technics, a protective sealed Ni-TiO2 composite coating (SCC) was prepared on sintered NdFeB permanent magnet by pulse current electrodeposition and sol-gel combined technique. For a comparison, unsealed Ni-TiO2 composite coating was also investigated. The potentiodynamic polarization and electrochemical impedance spectroscopy tests showed that SCC exhibited more excellent anticorrosive properties than UCC, and therefore provided better corrosion protection for sintered NdFeB permanent magnet. The electrochemical impedance spectroscopy (EIS) technique was employed to study the changes in electrochemical corrosion behaviors and failure mechanism of films or coatings in 3.5 wt.% NaCl corrosive media. The results of corrosion tests indicated that the evolution of electrochemical corrosion behavior of SCC could be divided into three stages. The first stage was the immersion time ranging from 1 h to 240 h in which three partially overlapped time constants could be observed and the impedance modulus|Z| of SCC remained at a very high value, suggesting the excellent protective properties provided for the substrate. The second stage was the immersion time ranging from 240 h to 264 h in which two well-defined time constants could be observed, and the impedance modulus |Z| of SCC decreased sharply. At the second stage, the SCC still provided good protection for the substrate. The third stage was the immersion time of 288 h in which only one well-defined time constant could be observed and the impedance modulus|Z| of SCC decreased more, and then the protective properties of SCC for substrate practically disappeared.
(2) A protective Ni-Co alloy coating was electrodeposited on sintered NdFeB permanent magnet applying electrodeposition technique. The microstructure, surface morphologies and chemical composition of coatings were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS), respectively. The corrosion protection properties of alloy coating for sintered NdFeB permanent magnet in neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Microstructure analysis showed that the microstructure of Ni-Co alloy coating was substitutional solid solution with the Co as solute and Ni as solvent, respectively; the addition of cobalt element into matrix metal Ni altered the preferential orientation of matrix metal Ni from (20 0) crystal face to (111) crystal face. Surface morphologies tests indicated that, compared with pure Ni coating, the surface morphologies of Ni-Co alloy coating were more compact and uniform due to the grain-refining. The results of potentiodynamic polarization test suggested that, compared with pure nickel coating, Ni-Co alloy coating exhibited much nobler corrosion potential (Econ) and lower corrosion current density (icon), indicating better anticorrosive properties. The long-term immersion test by dint of EIS indicated that the Ni-Co alloy coating still presented high impedance value of 1.9×1O5Ω·cm2 with the immersion time of 576 h suggesting the excellent anticorrosive properties. The corrosion protection properties of pure nickel coating provided for sintered NdFeB permanent magnet practically disappeared with the immersion time of 144 h, which also indicated that the Ni-Co alloy coating provided better corrosion protection properties for the sintered NdFeB permanent magnet compared with pure nickel coating.
(3) In order to further enlarge the application fields of sintered NdFeB permanent magnet, a protective Ni-Co-TiO2 composite coating was prepared on the sintered NdFeB permanent magnet by composite electrodeposition technique. The electrochemical corrosion behaviours of the composite coating in 0.5 mol L-1 H2SO4,0.6 mol L-1 NaOH,0.6 mol L-1 Na2SO4 and neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS), showing good corrosion, protection for sintered NdFeB permanent magnet in diverse corrosive media. In order to further investigate the protective properties of the composite coating for sintered NdFeB permanent magnet and the practicability of the composite coating, the long-term immersion test was carried out in neutral 3.5 wt.% NaCl corrosive media using EIS. The results of long-term corrosion test showed that the Ni-Co-TiO2 composite coating could provide long-term protection in neutral 3.5 wt.% NaCl corrosive media for sintered NdFeB permanent magnet due to the formation of passive film.
(4) Taking into account environment friendly, simplifying operation technics and reducing the technical cost, a anodic Zn-TiO2/Si sol gradient film (TZT), whose role in corrosion protection for sintered NdFeB permanent magnet was the combination of mechanical isolation and electrochemical protection, was prepared on sintered NdFeB permanent magnet by electrodeposition and sol-gel combined technique. The anticorrosive properties of TZT in neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) technique. In order to further study the corrosion protection of film, the immersion tests were employed in neutral 3.5 wt.% NaCl corrosive media. Comparing the surface morphlogies of TZT with the immersion time of 336 h with that of the Zn-TiO2 composite coating with the immersion time of 264 h, it can be seen that, due to the blocking effect of sealing layer, TZT could suppress the corrosion process by holding back the transfer or diffusion of corrosive media, and therefore showed the excellent corrosion protection properties for sintered NdFeB permanent magnet.
迄今为止所报道的关于烧结型NdFeB永磁体表面腐蚀保护膜层的研究主要侧重于工艺研究及其短期耐腐蚀性能测试,而对膜层在实际腐蚀环境中的腐蚀保护能力的长期跟踪测试、膜层电化学腐蚀行为变化、失效机理方面的探讨则鲜有报道。膜层对NdFeB磁体长期的腐蚀保护性能研究对于该磁体的广泛应用更具有指导意义。
基于以上问题,本文在研究和借鉴近年来国内外有关烧结型NdFeB永磁体及其它金属材料腐蚀研究方法的基础上,通过大量的正交试验,在烧结型NdFeB永磁体表面制备出多种具有优异耐腐蚀性能的膜层,并利用电化学极化、电化学阻抗谱和浸泡等测试跟踪膜层在实际腐蚀环境对永磁体的腐蚀保护能力的变化,分析和探讨了膜层的电化学腐蚀行为及失效机理。本论文通过电沉积和溶胶凝胶技术相结合的方法,首次制备了封孔的Ni-TiO2复合膜层、Ni-Co合金镀层、Ni-Co-TiO2合金复合镀层和硅烷处理的Zn-TiO2梯度膜层。本文的主要研究内容如下：
(1)以环境友好和操作工艺相对简易为前提,结合溶胶凝胶技术及脉冲电沉积技术,在烧结型NdFeB永磁体表面制备了密封的Ni-TiO2复合膜层(SCC)。作为对比,对未封孔的Ni-TiO2复合膜层(UCC)也做了相应研究。电化学阻抗和极化测试结果表明SCC具有比UCC更为优异的耐腐蚀性能,能够为烧结型NdFeB永磁体提供更好的腐蚀保护。为了更深入研究SCC对永磁体的实际保护性能,采用电化学阻抗谱技术测试及分析了SCC在中性3.5wt.%NaCl腐蚀介质长期浸泡过程中耐腐蚀性能的变化及失效机理。浸泡实验结果显示,SCC的电化学腐蚀行为分三个阶段。第一阶段是浸泡时间1 h到240 h,这一阶段观察到三个部分重叠的时间常数,此时SCC的阻抗模值|Z|仍然非常高,说明此阶段膜层可以对基体提供优异的腐蚀保护。第二阶段是浸泡时间240 h到264 h,该阶段观察到两个明显的时间常数,且SCC的阻抗模值|Z|急剧下降,但SCC仍然对基体提供了良好的保护。第三阶段是浸泡时间达到288 h,此阶段只观察到一个明显的时间常数,同时SCC的阻抗模值|Z|下降更多,表明SCC对基体的腐蚀保护作用已经消失。
(2)应用电沉积技术在烧结型NdFeB永磁体表面制备了耐腐蚀性能优异的Ni-Co合金镀层。采用扫描电子显微镜(SEM)、能量散射谱(EDS)、X射线衍射(XRD)、动电位极化曲线、电化学阻抗谱(EIS)和浸泡腐蚀等测试手段表征该合金镀层的微观结构、形貌及耐腐蚀性能。微观结构分析表明,Ni-Co合金镀层是溶质原子(Co原子)占据溶剂(Ni原子)晶格中的结点位置而形成的置换固溶体(fcc)；Ni基质金属中Co元素的添加,导致了Ni基质金属的择优取向从(200)晶面变为(111)晶面。表面形貌测试说明,由于Ni-Co合金镀层晶粒发生细化,所以具有比纯镍镀层更为致密的形貌；动电位测试结果显示,Ni-Co合金镀层具有比纯镍镀层更正的腐蚀电位(Econ),更小的腐蚀电流密度(icon)；EIS的长期浸泡实验结果表明该合金镀层在浸泡576 h后对基体仍具有良好的腐蚀保护能力,而纯镍镀层在浸泡144 h小时后,其腐蚀保护能力已经丧失。这进一步揭示了Ni-Co合金镀层比纯镍镀层有更好的耐腐蚀性能。
(3)为了进一步扩大烧结型NdFeB永磁体使用范围,本论文运用复合电沉积方法在烧结型NdFeB永磁材料表面制备了Ni-Co-TiO2复合镀层。通过EIS和电化学极化测试研究了该镀层在0.5 mol L-1 H2SO4, 0.6 mol L-1 NaOH,0.6 mol L-1 Na2SO4和中性的3.5wt.%NaCl腐蚀介质中的电化学腐蚀行为。实验结果表明,该复合镀层在多种腐蚀介质中对永磁体均具有良好的腐蚀保护性能。为了更深入研究该镀层的腐蚀保护能力及实用性,本文采用EIS研究了Ni-Co-TiO2合金复合镀层在中性3.5wt.%NaCl腐蚀介质长期浸泡过程中的电化学腐蚀行为变化及其原因。长期浸泡实验结果揭示了在3.5wt.%NaCl腐蚀环境中该复合镀层能够为烧结型NdFeB永磁体提供长期腐蚀保护的原因：Ni-Co-TiO2复合镀层表面生成了钝化膜。
(4)以环境友好、操作工艺相对简化和降低工艺成本为前提,结合溶胶凝胶技术和电沉积技术,在烧结型NdFeB永磁体表面制备了具有机械隔离和电化学保护的双重腐蚀保护作用的膜层,即阳极性Zn-TiO2硅溶胶梯度膜层(TZT)。利用电化学阻抗谱和极化测试研究了TZT在中性3.5wt.%NaCl腐蚀介质中的耐腐蚀性能。为了进一步研究TZT的耐腐蚀性能,在中性3.5wt.%NaCl腐蚀介质中进行了长期浸泡实验。对比Zn-TiO2镀层浸泡264 h及TZT浸泡336h后的表面腐蚀形貌发现,由于溶胶层对腐蚀介质的阻挡作用,使腐蚀介质的传输受到阻碍,TZT显示出更好的耐腐蚀性能,从而对烧结型NdFeB永磁体提供了更好的腐蚀保护。
The sintered NdFeB (neodymium-iron-boron) permanent magnet as the third-era permanent magnet, which exhibits excellent magnetic properties such as high remanence, high coercivity, large energy product, good machinability and comparatively low price, has been used for many applications in various fields such as acoustics, aviation, electronics, automation, biomedical and communications. However, the anticorrosive properties of sintered NdFeB permanent magnet are very poor, and easily form the galvanic corrosion in corrosive media and humid environment, which results in the changes in the composition and microstructure of magnet, and then the decline of the magnetism. This severely impedes and limits the extensive application of NdFeB magnet in various fields. The anticorrosive properties of NdFeB magnet have become a key index to estimate its application properties. Therefore, it is very important to improve the corrosion resistance of NdFeB permanent magnets.
So far, most of the researches on the corrosion protection of sintered NdFeB permanent magnet were emphasizing particularly on the investigation on technical study and tests of the short-term protective properties of coatings or films prepared on sintered NdFeB permanent magnet in corrosive media. Unfortunately, few works were focusing on the tests of the long-term anticorrosive properties and the changes in electrochemical corrosion behaviors in corrosive media, as well as the failure mechanism, which may be an indicator of the actual corrosion protection properties of coatings or films provided for sintered NdFeB permanent magnet.
Based on the problems mentioned above, different films or coatings possessed excellent anticorrosive properties were prepared by dint of large numbers of orthogonal experiments, which were on the basis of the investigation on the corrosion protection of sintered NdFeB permanent magnet and other metals. The potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) techniques and immersion tests were employed to study the changes in the actual corrosion protection properties of films or coatings provided for permanent magnet in service environment. Sealed Ni-TiO2 composite coating, Ni-Co alloy coating, Ni-Co-TiO2 composite coating and silicane treated Zn-TiO2 grade film were firstly prepared on sintered NdFeB permanent magnet by the combination of electrodeposition and sol-gel methods. The major research works in the present study are as follows:
(1) Taking into account environment friendly and simplifying operation technics, a protective sealed Ni-TiO2 composite coating (SCC) was prepared on sintered NdFeB permanent magnet by pulse current electrodeposition and sol-gel combined technique. For a comparison, unsealed Ni-TiO2 composite coating was also investigated. The potentiodynamic polarization and electrochemical impedance spectroscopy tests showed that SCC exhibited more excellent anticorrosive properties than UCC, and therefore provided better corrosion protection for sintered NdFeB permanent magnet. The electrochemical impedance spectroscopy (EIS) technique was employed to study the changes in electrochemical corrosion behaviors and failure mechanism of films or coatings in 3.5 wt.% NaCl corrosive media. The results of corrosion tests indicated that the evolution of electrochemical corrosion behavior of SCC could be divided into three stages. The first stage was the immersion time ranging from 1 h to 240 h in which three partially overlapped time constants could be observed and the impedance modulus|Z| of SCC remained at a very high value, suggesting the excellent protective properties provided for the substrate. The second stage was the immersion time ranging from 240 h to 264 h in which two well-defined time constants could be observed, and the impedance modulus |Z| of SCC decreased sharply. At the second stage, the SCC still provided good protection for the substrate. The third stage was the immersion time of 288 h in which only one well-defined time constant could be observed and the impedance modulus|Z| of SCC decreased more, and then the protective properties of SCC for substrate practically disappeared.
(2) A protective Ni-Co alloy coating was electrodeposited on sintered NdFeB permanent magnet applying electrodeposition technique. The microstructure, surface morphologies and chemical composition of coatings were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS), respectively. The corrosion protection properties of alloy coating for sintered NdFeB permanent magnet in neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Microstructure analysis showed that the microstructure of Ni-Co alloy coating was substitutional solid solution with the Co as solute and Ni as solvent, respectively; the addition of cobalt element into matrix metal Ni altered the preferential orientation of matrix metal Ni from (20 0) crystal face to (111) crystal face. Surface morphologies tests indicated that, compared with pure Ni coating, the surface morphologies of Ni-Co alloy coating were more compact and uniform due to the grain-refining. The results of potentiodynamic polarization test suggested that, compared with pure nickel coating, Ni-Co alloy coating exhibited much nobler corrosion potential (Econ) and lower corrosion current density (icon), indicating better anticorrosive properties. The long-term immersion test by dint of EIS indicated that the Ni-Co alloy coating still presented high impedance value of 1.9×1O5Ω·cm2 with the immersion time of 576 h suggesting the excellent anticorrosive properties. The corrosion protection properties of pure nickel coating provided for sintered NdFeB permanent magnet practically disappeared with the immersion time of 144 h, which also indicated that the Ni-Co alloy coating provided better corrosion protection properties for the sintered NdFeB permanent magnet compared with pure nickel coating.
(3) In order to further enlarge the application fields of sintered NdFeB permanent magnet, a protective Ni-Co-TiO2 composite coating was prepared on the sintered NdFeB permanent magnet by composite electrodeposition technique. The electrochemical corrosion behaviours of the composite coating in 0.5 mol L-1 H2SO4,0.6 mol L-1 NaOH,0.6 mol L-1 Na2SO4 and neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS), showing good corrosion, protection for sintered NdFeB permanent magnet in diverse corrosive media. In order to further investigate the protective properties of the composite coating for sintered NdFeB permanent magnet and the practicability of the composite coating, the long-term immersion test was carried out in neutral 3.5 wt.% NaCl corrosive media using EIS. The results of long-term corrosion test showed that the Ni-Co-TiO2 composite coating could provide long-term protection in neutral 3.5 wt.% NaCl corrosive media for sintered NdFeB permanent magnet due to the formation of passive film.
(4) Taking into account environment friendly, simplifying operation technics and reducing the technical cost, a anodic Zn-TiO2/Si sol gradient film (TZT), whose role in corrosion protection for sintered NdFeB permanent magnet was the combination of mechanical isolation and electrochemical protection, was prepared on sintered NdFeB permanent magnet by electrodeposition and sol-gel combined technique. The anticorrosive properties of TZT in neutral 3.5 wt.% NaCl corrosive media were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) technique. In order to further study the corrosion protection of film, the immersion tests were employed in neutral 3.5 wt.% NaCl corrosive media. Comparing the surface morphlogies of TZT with the immersion time of 336 h with that of the Zn-TiO2 composite coating with the immersion time of 264 h, it can be seen that, due to the blocking effect of sealing layer, TZT could suppress the corrosion process by holding back the transfer or diffusion of corrosive media, and therefore showed the excellent corrosion protection properties for sintered NdFeB permanent magnet.
引文
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