CN103334143B - A kind of Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast - Google Patents
A kind of Zr alloy surface prepares the differential arc oxidation method of wear-resisting zirconia and aluminum oxide mixed coating fast Download PDFInfo
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Abstract
本发明涉及电化学领域,公开了一种锆合金表面快速制备耐磨氧化锆和氧化铝混合涂层的微弧氧化方法,具体步骤为:以预处理后的锆合金做阳极,钢板做阴极,控制电解液温度为10℃-30℃,设置微弧氧化电源参数,打开电源,处理2min-12min,关闭电源,取出锆合金,用去离子水冲洗表面,即得;所述电解液的组成为:铝酸钠30g-60g,强碱1g-10g,去离子水1000ml。方法成膜速度快,膜层结构均匀,含有大量氧化铝;膜层耐磨性远远超过一般的锆合金在低浓度铝酸盐和磷酸盐等电解液中得到的微弧氧化膜。The invention relates to the field of electrochemistry, and discloses a micro-arc oxidation method for quickly preparing a wear-resistant zirconia and alumina mixed coating on the surface of a zirconium alloy. The specific steps are: use the pretreated zirconium alloy as the anode, and the steel plate as the cathode, Control the temperature of the electrolyte to 10°C-30°C, set the parameters of the micro-arc oxidation power supply, turn on the power, process for 2min-12min, turn off the power, take out the zirconium alloy, rinse the surface with deionized water, and the composition of the electrolyte is as follows: : Sodium aluminate 30g-60g, strong alkali 1g-10g, deionized water 1000ml. The film forming speed of the method is fast, the structure of the film layer is uniform, and contains a large amount of alumina; the wear resistance of the film layer far exceeds that of the micro-arc oxidation film obtained by the general zirconium alloy in the electrolyte solution such as low concentration aluminate and phosphate.
Description
技术领域technical field
本发明涉及电化学领域,进一步是指锆合金表面快速制备耐磨ZrO2/Al2O3混合涂层的微弧氧化方法。The invention relates to the field of electrochemistry, and further refers to a micro-arc oxidation method for rapidly preparing a wear-resistant ZrO 2 /Al 2 O 3 mixed coating on the surface of a zirconium alloy.
背景技术Background technique
锆合金是一种阀金属,以其突出的核性能良好的耐蚀性、生物相容性等被广泛应用于高科技技术领域,由于锆合金的热中子吸收截面低,有良好的抗中子辐照能力,与UO2有良好的相容性,且在高温高压水和蒸汽中耐腐蚀良好,以及具有合适的强度和延展性、足够的高温强度等特点。因此,被普遍用作核动力堆的燃料包壳和堆内结构部件。并且锆合金在人体植入材料领域也具有很重要的价值。但锆合金的耐磨性能低于不锈钢、镍合金等其他核工业用材料,且锆合金服役的核反应堆内的工况条件十分恶劣,受高温高压水、强烈的中子辐照、电化学、复杂的机械应力以及核燃料的裂变气体等的影响,面临着很严重的腐蚀及摩擦情况,所以对锆合金的摩擦及其耐腐蚀性提出了很高的要求。此外在生物医学领域,如全髋关节置换术(totalhiparthroplasty,THA)、全膝关节置换术(TotalKneearthroplastyTKA)中,植入材料受到很高的载荷(人体自重),迫切需要提高锆合金的耐磨能力。微弧氧化技术可以在锆合金表面生成不同厚度的氧化膜,极大地提高锆合金的耐磨、耐蚀性能。Zirconium alloy is a kind of valve metal, which is widely used in high-tech technical fields due to its outstanding nuclear properties, good corrosion resistance and biocompatibility. Sub - irradiation ability, good compatibility with UO2, and good corrosion resistance in high temperature and high pressure water and steam, as well as suitable strength and ductility, sufficient high temperature strength and other characteristics. Therefore, it is widely used as fuel cladding and internal structural components of nuclear power reactors. And zirconium alloys are also of great value in the field of human implant materials. However, the wear resistance of zirconium alloys is lower than that of stainless steel, nickel alloys and other nuclear industry materials, and the working conditions in nuclear reactors where zirconium alloys are in service are very harsh, subject to high temperature and high pressure water, strong neutron irradiation, electrochemical, complex Due to the influence of mechanical stress and fission gas of nuclear fuel, etc., it faces very serious corrosion and friction conditions, so high requirements are put forward for the friction and corrosion resistance of zirconium alloys. In addition, in the field of biomedicine, such as total hip arthroplasty (THA) and total knee arthroplasty (Total Knearthroplasty TKA), implant materials are subject to high loads (body weight), and there is an urgent need to improve the wear resistance of zirconium alloys. . Micro-arc oxidation technology can generate oxide films of different thicknesses on the surface of zirconium alloys, which greatly improves the wear resistance and corrosion resistance of zirconium alloys.
微弧氧化技术又称等离子电解氧化(Plasmaelectrolyticoxidation),是从传统阳极氧化基础上发展起来的一种的新型表面改性技术,该技术源于100多年前电解过程的火花放电现象的发现,但其实际应用直到上世纪60到70年代才由前苏联学者开发利用,其后德国、美国、中国等国的科学家也进行了早期研究。该技术运用于铝、镁合金的研究较多,但对锆合金来说研究较少,该技术目前仍是国际研究的热点。同其他表面处理技术相比,等离子电解氧化具有以下明显优势:Micro-arc oxidation technology, also known as plasma electrolytic oxidation, is a new type of surface modification technology developed on the basis of traditional anodic oxidation. This technology originated from the discovery of the spark discharge phenomenon in the electrolysis process more than 100 years ago, but Practical applications were not developed and utilized by former Soviet scholars until the 1960s and 1970s, and then scientists in Germany, the United States, China and other countries also conducted early research. There are many studies on the application of this technology to aluminum and magnesium alloys, but less research on zirconium alloys. This technology is still a hot spot in international research. Compared with other surface treatment technologies, plasma electrolytic oxidation has the following obvious advantages:
(1)等离子电解氧化技术可用于各种复杂形状的工件。(1) Plasma electrolytic oxidation technology can be used for workpieces of various complex shapes.
(2)等离子电解氧化膜在金属表面原位生长,膜层与基体金属结合力好,不易脱落。(2) The plasma electrolytic oxidation film grows in situ on the metal surface, and the film layer has good bonding force with the base metal and is not easy to fall off.
(3)膜层厚度受处理时间控制,最大可达200-300μm。(3) The thickness of the film layer is controlled by the processing time, and the maximum can reach 200-300 μm.
(4)装置简单,占地面积小。工艺流程简单,易操作。前处理工序少,处理效率高,适合自动化生产。(4) The device is simple and occupies a small area. The technological process is simple and easy to operate. Less pre-treatment process, high processing efficiency, suitable for automatic production.
(5)电解液可以重复使用,对环境污染少,符合当今环保要求。(5) The electrolyte solution can be reused, has little environmental pollution, and meets current environmental protection requirements.
在核工业领域,锆合金材料表面的氧化膜不宜太厚(而在其他领域的应用没有这个要求),因为氧化锆的热导率低,将会影响核反应堆的包壳材料的导热性能,因此有必要开发锆合金表面的高性能薄的膜层。In the field of nuclear industry, the oxide film on the surface of zirconium alloy materials should not be too thick (but there is no such requirement in other fields of application), because the thermal conductivity of zirconia is low, which will affect the thermal conductivity of the cladding material of the nuclear reactor, so there is It is necessary to develop high performance thin film layers on zirconium alloy surfaces.
氧化锆有三种晶型:立方相(c-ZrO2)、四方相(t-ZrO2)和单斜相(m-ZrO2)。前两种是高温相,单斜相是室温稳定相。四方相在一定的条件下也可以在常温存在。微弧氧化膜中常常会存在一定量的四方相和单斜相。四方相向单斜相转变属于马氏体相变,会产生体积膨胀,因此,含有单斜相的膜层中往往会存在微裂纹,从而影响微弧氧化膜的性能。如果能使四方相在常温下稳定下来,将会减少膜层的裂纹从而提高膜层的耐磨性。Zirconia has three crystal forms: cubic (c-ZrO 2 ), tetragonal (t-ZrO 2 ) and monoclinic (m-ZrO 2 ). The first two are high-temperature phases, and the monoclinic phase is a stable phase at room temperature. The tetragonal phase can also exist at room temperature under certain conditions. A certain amount of tetragonal phase and monoclinic phase often exist in the micro-arc oxidation film. The transformation from the tetragonal phase to the monoclinic phase belongs to the martensitic phase transition, which will cause volume expansion. Therefore, microcracks often exist in the film layer containing the monoclinic phase, which affects the performance of the micro-arc oxidation film. If the tetragonal phase can be stabilized at room temperature, the cracks of the film layer will be reduced and the wear resistance of the film layer will be improved.
目前,国内外研究者关于锆合金微弧氧化的文献不少,但普遍采用硅酸盐、磷酸盐等为主,得到的涂层相结构主要为单斜相氧化锆和少量四方相氧化锆组成。根据我们最近的研究论文([1]Y.Cheng,F.Wu,J.Dong,X.Wu,Z.Xue,E.Matykina,P.Skeldon,G.E.Thompson,Comparisonofplasmaelectrolyticoxidationofzirconiumalloyinsilicate-andaluminate-basedelectrolytesandwearpropertiesoftheresultingcoatings,Electrochim.Acta85(2012)25),铝酸钠电解液有利于得到四方相为主的膜层。但是在研究论文[1]中,使用的电解液为6gl-1NaAlO2和8gl-1Na4P2O7·10H2O的混合溶液。该电解液的缺点是铝酸钠浓度低,不能生成含有大量氧化铝(Al2O3)的膜层,由于膜层中Al含量低(原子百分含量为3-10at%左右),而且,膜层内外层差别较大。此外由于电解液含有磷酸盐(Na4P2O7·10H2O)成分,导致膜层生长到一定厚度(30微米)后,发生机械剥离,不能生成更厚的膜层,而在耐磨性要求高的场合(如生物植入材料),需要有一定厚度的膜层。At present, there are many literatures on micro-arc oxidation of zirconium alloys by researchers at home and abroad, but silicates and phosphates are generally used, and the obtained coating phase structure is mainly composed of monoclinic zirconia and a small amount of tetragonal zirconia. . According to our recent research paper ([1] Y.Cheng, F.Wu, J.Dong, X.Wu, Z.Xue, E.Matykina, P.Skeldon, GEThompson, Comparisonofplasmaelectrolyticoxidationofzirconiumalloyinsilicate-andaluminate-basedelectrolytesandwearpropertiesoftheresultingcoatings, Electrochim.Acta85( 2012) 25), the sodium aluminate electrolyte is beneficial to obtain a tetragonal phase-based film layer. But in the research paper [1], the electrolyte used is a mixed solution of 6gl -1 NaAlO 2 and 8gl -1 Na 4 P 2 O 7 ·10H 2 O. The disadvantage of this electrolytic solution is that the concentration of sodium aluminate is low, and a film layer containing a large amount of aluminum oxide (Al 2 O 3 ) cannot be generated, because the Al content in the film layer is low (the atomic percentage is about 3-10 at%), and, There is a large difference between the inner and outer layers of the film layer. In addition, because the electrolyte contains phosphate (Na 4 P 2 O 7 10H 2 O) components, after the film layer grows to a certain thickness (30 microns), mechanical peeling occurs, and a thicker film layer cannot be formed. For occasions with high performance requirements (such as biological implant materials), a film layer with a certain thickness is required.
另外,微弧氧化膜的性能和电参数的关系也很大,高频脉冲的电流制度优于直流或低频的电流制度。采用铝酸钠为电解液进行微弧氧化目前研究报道较少,西安交通大学的研究人员曾在0.2-0.35M(相当于16.4g/L到28.7g/L)的铝酸钠溶液中对纯锆进行微弧氧化([Y.Yan,Y.Han,D.Li,J.Huang,Q.Lian,EffectofNaAlO2concentrationonmicrostructureandcorrosionresistanceofAl2O3/ZrO2coatingsformedonzirconiumbymicro-arcoxidation,AppliedSurfaceScience256(2010)6359],采用的电流制度是100Hz的低频脉冲电流,在得到的微弧氧化膜中单斜相氧化锆仍然占有较大的分数。而且,他们得出的结论是铝酸钠浓度提高到0.35M(28.7g/L)时氧化膜的性能下降。In addition, the performance of the micro-arc oxidation film has a great relationship with the electrical parameters, and the high-frequency pulse current system is better than the DC or low-frequency current system. Using sodium aluminate as the electrolyte for micro-arc oxidation is currently less reported. Researchers from Xi'an Jiaotong University once tested pure Micro-arc oxidation of zirconium ([Y.Yan, Y.Han, D.Li, J.Huang, Q.Lian, Effect of NaAlO2 concentration on microstructure and corrosion resistance of Al 2 O 3 /ZrO 2 coatings formed on zirconium by micro-arcoxidation, Applied Surface Science 256 (2010) 6359], the current system used is 100Hz low-frequency pulse current, monoclinic zirconia still occupies a large fraction in the obtained micro-arc oxidation film. Moreover, they concluded that when the concentration of sodium aluminate increased to 0.35M (28.7g/L), the oxidation Membrane performance degrades.
最后,微弧氧化是一个高耗能的技术,要达到一定厚度的膜层,常规的微弧氧化的时间为30分钟到1个小时不等。如果成膜过程较慢,将在过程中大量放热,造成能量损失、能耗大,因此,快速成膜在提高微弧氧化的能耗效率方面具有决定性的意义,如果能够快速成膜,将极大的降低该技术的能耗,对于推广该技术也有积极的意义。Finally, micro-arc oxidation is a high-energy-consuming technology. To achieve a certain thickness of the film, the conventional micro-arc oxidation takes 30 minutes to 1 hour. If the film forming process is slow, a large amount of heat will be released during the process, resulting in energy loss and high energy consumption. Therefore, fast film forming is of decisive significance in improving the energy consumption efficiency of micro-arc oxidation. Greatly reducing the energy consumption of this technology also has positive significance for popularizing this technology.
发明内容Contents of the invention
针对目前国内外关于研究微弧氧化涂层技术存在的不足进行改进,目前国内外微弧氧化多采用磷酸盐、硅酸盐为电解液,得到的膜层为单斜和四方相的混合膜层,其耐磨性较差,此外对于前面提到的低浓度的铝酸钠中得到的膜层(研究论文[1]),仍然存在一系列缺点:如膜中氧化铝的含量偏低,膜层结构分为内外层,成分不均一,处理时间长的膜层存在机械剥离现象,不能形成厚的膜层等问题。本发明旨在提供一种快速制备耐磨氧化锆和氧化铝混合涂层的微弧氧化方法,该方法选用高浓度铝酸钠为主的电解液,在特定的电流参数下,稳定了锆合金膜层中的四方相,形成均一的氧化铝/氧化锆混合膜层,耐磨性能得到有效提高。该发明在核工业领域和生物材料领域有重要的应用价值。In order to improve the deficiencies in the research of micro-arc oxidation coating technology at home and abroad, phosphate and silicate are mostly used as electrolytes in micro-arc oxidation at home and abroad, and the obtained film layer is a mixed film layer of monoclinic and tetragonal phases. , its wear resistance is poor. In addition, there are still a series of shortcomings for the film layer obtained from the aforementioned low concentration of sodium aluminate (research paper [1]): such as the low content of alumina in the film, the film The layer structure is divided into inner and outer layers, and the composition is not uniform. There are problems such as mechanical peeling of the film layer for a long time, and the inability to form a thick film layer. The present invention aims to provide a micro-arc oxidation method for quickly preparing wear-resistant zirconia and alumina mixed coatings. The method uses high-concentration sodium aluminate as the main electrolyte, and stabilizes the zirconium alloy under specific current parameters. The tetragonal phase in the film layer forms a uniform alumina/zirconia mixed film layer, and the wear resistance is effectively improved. The invention has important application value in the fields of nuclear industry and biomaterials.
为达到上述目的,本发明所采用的技术方案是:In order to achieve the above object, the technical scheme adopted in the present invention is:
锆合金表面快速制备耐磨氧化锆和氧化铝混合涂层的微弧氧化方法,具体步骤为:以预处理后的锆合金做阳极,钢板做阴极,控制电解液温度为10℃-30℃,设置微弧氧化电源参数,打开电源,处理2min-12min,关闭电源,取出锆合金,用去离子水冲洗表面,即得;A micro-arc oxidation method for rapid preparation of wear-resistant zirconia and alumina mixed coatings on the surface of zirconium alloys. The specific steps are: use pretreated zirconium alloys as anodes, steel plates as cathodes, and control the temperature of the electrolyte at 10°C-30°C. Set the parameters of the micro-arc oxidation power supply, turn on the power, process for 2min-12min, turn off the power, take out the zirconium alloy, rinse the surface with deionized water, and you get it;
所述电解液的组成为:铝酸钠30g-60g,强碱1g-10g,去离子水1000ml;The composition of the electrolyte is: sodium aluminate 30g-60g, strong alkali 1g-10g, deionized water 1000ml;
所述微弧氧化电源参数设置为:正电流密度为5-30A/dm2内的一恒定值,负电流密度为5-30A/dm2内的一恒定值;频率:500Hz-5000Hz;正负占空比:5%-30%。The parameters of the micro-arc oxidation power supply are set as follows: the positive current density is a constant value within 5-30A /dm2, and the negative current density is a constant value within 5-30A /dm2; frequency: 500Hz-5000Hz; positive and negative Duty cycle: 5%-30%.
所述电解液温度优选为20℃-30℃。The electrolyte temperature is preferably 20°C-30°C.
所述强碱优选为氢氧化钠或氢氧化钾。The strong base is preferably sodium hydroxide or potassium hydroxide.
所述微弧氧化电源参数设置优选为:正电流密度为10-15A/dm2内的一恒定值,负电流密度为10-15A/dm2内的一恒定值;频率:1000Hz-3000Hz;正负占空比:20%-30%。The parameters of the micro-arc oxidation power supply are preferably set as follows: positive current density is a constant value within 10-15A /dm2, negative current density is a constant value within 10-15A/dm2; frequency: 1000Hz-3000Hz; positive current density is a constant value within 10-15A/dm2 ; Negative duty cycle: 20%-30%.
所述处理的时间优选为2min(要求薄膜的场合)-10min(要求厚膜的场合)。The processing time is preferably 2 min (when a thin film is required) to 10 min (when a thick film is required).
所述锆合金的预处理过程优选为:先用金相砂纸把表面打磨,然后依次用水洗,酒精超声清洗,去离子水洗,再用E-44环氧树脂密封,最后将参与反应的锆合金表面用金相砂纸打磨。The pretreatment process of the zirconium alloy is preferably as follows: firstly, the surface is polished with metallographic sandpaper, then washed with water, alcohol ultrasonic cleaning, deionized water, and then sealed with E-44 epoxy resin, and finally the zirconium alloy participating in the reaction The surface is polished with metallographic sandpaper.
下面对本发明做进一步的解释和说明:The present invention is further explained and illustrated below:
微弧氧化的原理本质上是一种高电压下的阳极氧化,属于电化学领域,但由于使用的电压高于金属表面氧化膜的击穿电压,会在处理时在金属表面产生等离子体火花,因此,微弧氧化的过程涉及化学反应、电化学反应以及等离子体反应,其机理很复杂。微弧氧化膜层的质量和电解液成分、金属本身以及电参数有很大的关系。有关微弧氧化技术的电参数,可以是直流也可以是交流。早期微弧氧化技术多为直流,随着电源技术的发展,交流或脉冲电源成为主流。因为后者可以通过调节占空比、正负脉冲的比率等对放电过程提供更好的控制,避免长时间火花放电对膜层的危害。而电解液对微弧氧化膜层的质量更具有决定性的作用。本发明的主要创新之处有以下两点:The principle of micro-arc oxidation is essentially an anodic oxidation under high voltage, which belongs to the field of electrochemistry. However, since the voltage used is higher than the breakdown voltage of the oxide film on the metal surface, plasma sparks will be generated on the metal surface during processing. Therefore, the process of micro-arc oxidation involves chemical reaction, electrochemical reaction and plasma reaction, and its mechanism is very complicated. The quality of the micro-arc oxidation film has a great relationship with the composition of the electrolyte, the metal itself and the electrical parameters. The electrical parameters related to the micro-arc oxidation technology can be DC or AC. The early micro-arc oxidation technology was mostly DC. With the development of power supply technology, AC or pulse power supply became the mainstream. Because the latter can provide better control over the discharge process by adjusting the duty cycle, the ratio of positive and negative pulses, etc., and avoid the damage of the film layer caused by long-term spark discharge. The electrolyte has a more decisive effect on the quality of the micro-arc oxidation film. The main innovation of the present invention has the following two points:
(1)通过在高浓度的铝酸盐溶液中进行微弧氧化,极大地提高了微弧氧化膜的生长速度(2min就可生成10μm左右的膜层),降低了微弧氧化过程的能耗。(1) By performing micro-arc oxidation in a high-concentration aluminate solution, the growth rate of the micro-arc oxidation film is greatly improved (a film layer of about 10 μm can be formed in 2 minutes), and the energy consumption of the micro-arc oxidation process is reduced. .
(2)成功在锆合金的氧化膜中大量掺入高硬度的氧化铝(铝的原子分数可达15-40at%),而且改变了膜层的微观结构(形成组成均一的膜层,避免了低浓度铝酸盐中内外层不均匀的现象),从而极大的提升了膜层的耐磨性能(膜层耐磨性远高于低浓度铝酸盐中得到的膜层)。(2) A large amount of high-hardness alumina (atomic fraction of aluminum can reach 15-40at%) has been successfully mixed into the oxide film of zirconium alloy, and the microstructure of the film layer has been changed (forming a uniform film layer, avoiding the The phenomenon of uneven inner and outer layers in low-concentration aluminate), which greatly improves the wear resistance of the film layer (the wear resistance of the film layer is much higher than that obtained in low-concentration aluminate).
本发明在膜层中引入大量高性能氧化铝陶瓷相,极大的提高了锆合金的耐磨性,且锆合金成膜速度也得到极大提高,在高浓度(32gl-1)的铝酸钠溶液中处理2分钟可得10.3微米左右的膜层,而在磷酸盐溶液中,生成同样厚度的膜层至少需要30分钟。该膜层相比于磷酸盐中得到的同样厚度的膜层,其耐磨性能提高了将近16倍。在高浓度铝酸钠中处理10分钟可得65微米左右膜层(而在文献[1]中,处理10min的膜层厚度为30微米左右),其耐磨性比低浓度的铝酸钠中得到的相近厚度锆合金微弧氧化膜也有很大幅度的提高。The present invention introduces a large number of high - performance alumina ceramic phases into the film layer, which greatly improves the wear resistance of the zirconium alloy, and the film-forming speed of the zirconium alloy is also greatly improved. Treat in sodium solution for 2 minutes to get a film layer of about 10.3 microns, while in phosphate solution, it takes at least 30 minutes to form a film layer of the same thickness. Compared with the film layer of the same thickness obtained in phosphate, the wear resistance of the film layer is increased by nearly 16 times. A film layer of about 65 microns can be obtained by treating it in high-concentration sodium aluminate for 10 minutes (while in the literature [1], the thickness of the film layer treated for 10 minutes is about 30 microns), and its wear resistance is better than that in low-concentration sodium aluminate. The zirconium alloy micro-arc oxidation film with similar thickness is also greatly improved.
本发明的方法可以形成组成均一的膜层,所得到的锆合金微弧氧化膜由四方相氧化锆、γ-氧化铝以及非晶态氧化铝组成。The method of the invention can form a film layer with uniform composition, and the obtained zirconium alloy micro-arc oxidation film is composed of tetragonal phase zirconia, gamma-alumina and amorphous alumina.
本发明电解液中含有高浓度的铝酸钠溶液,使机械性能更好的氧化铝陶瓷(氧化铝的硬度是氧化锆的2到3倍)掺入微弧氧化膜,极大地提高微弧氧化膜的性能。本发明中得到的高氧化铝含量的微弧氧化膜与低氧化铝含量的微弧氧化膜相比,其膜层性能相对好很多。The electrolytic solution of the present invention contains a high-concentration sodium aluminate solution, so that alumina ceramics with better mechanical properties (the hardness of alumina is 2 to 3 times that of zirconia) is mixed into the micro-arc oxidation film, which greatly improves the micro-arc oxidation. Membrane performance. Compared with the micro-arc oxidation film with low alumina content, the micro-arc oxidation film with high alumina content obtained in the present invention has much better film performance.
本发明中涂层性能特征的检测需要用到以下仪器设备:The detection of coating performance characteristics among the present invention needs to use following equipment:
TT260履层测厚仪:北京时代之峰科技有限公司。可用来测量膜层的厚度。TT260 Layer Thickness Gauge: Beijing Times Peak Technology Co., Ltd. Can be used to measure the thickness of the film layer.
环境扫描电子显微镜及能谱仪:(SEM,QUANTA2000,FEI,USA):观察涂层微观形貌并进行成分分析。Environmental scanning electron microscope and energy dispersive spectrometer: (SEM, QUANTA2000, FEI, USA): observe the microscopic morphology of the coating and conduct component analysis.
X射线衍射仪:(产地日本,型号为RigakuD/MAX2500)。检测膜层相的组成。X-ray diffractometer: (produced in Japan, model RigakuD/MAX2500). Detect the composition of the film phase.
CETRUMT-3摩擦仪:采用球-快式摩擦试验,检测样品耐磨性。CETRUMT-3 Tribometer: Use ball-quick friction test to test the wear resistance of samples.
光学轮廓仪(WykoNT9100,VEECOInstrumentsInc.):检测磨痕深度与现有技术相比,本发明的优势是:Optical profiler (WykoNT9100, VEECO Instruments Inc.): Compared with the prior art for detecting the depth of wear scars, the advantages of the present invention are:
①本发明中,膜层生长速度快,采用了本发明的高浓度铝酸盐(32g/LNaAlO2)、以及低浓度铝酸盐(8g/LNaAlO2)以及磷酸盐电解液中进行微弧氧化处理,结果见图1。可以看出,采用高浓度铝酸钠极大的提高了膜层生长速度。其生长速度远远超过磷酸盐电解液膜层生长速度,此外,比低浓度铝酸盐中膜层生长厚度也快2倍左右。①In the present invention, the growth rate of the film layer is fast, and the high-concentration aluminate (32g/LNaAlO 2 ) and low-concentration aluminate (8g/LNaAlO 2 ) of the present invention are used to carry out micro-arc oxidation in the phosphate electrolyte processing, the results are shown in Figure 1. It can be seen that the use of high-concentration sodium aluminate greatly improves the growth rate of the film layer. Its growth rate far exceeds the growth rate of the phosphate electrolyte film layer. In addition, it is about 2 times faster than the growth thickness of the film layer in low-concentration aluminate.
②本发明中,膜层结构为均匀的单层结构,没有大的孔洞和裂纹,处理时间短的样品表面光滑。相组成为四方相氧化锆、γ-氧化铝和非晶态氧化铝。膜层中铝的原子分数可达15-40at%,远高于低浓度铝酸盐溶液中得到的膜层中的Al含量(如背景技术中所述研究论文[1]的膜层,其铝含量为3-10at%)。② In the present invention, the film layer structure is a uniform single-layer structure without large holes and cracks, and the surface of the sample with short processing time is smooth. The phase composition is tetragonal zirconia, γ-alumina and amorphous alumina. The atomic fraction of aluminum in the film layer can reach 15-40at%, which is much higher than the Al content in the film layer obtained in the low-concentration aluminate solution (as the film layer of the research paper [1] described in the background technology, its aluminum The content is 3-10at%).
③本发明中,膜层耐磨性能非常强,对反应10min生成的65.4微米厚度的试样,与背景技术中所述研究论文[1]相比,在10N载荷,30min的摩擦条件下,论文[1]中磨痕深度约为20μm,而本发明中的磨痕深度仅为10μm左右。并且,本发明的10min膜层可用30N的力摩擦30min,摩擦深度仅为20μm,而在背景技术中所述研究论文[1]中的低浓度铝酸盐中得到的膜层在30N的载荷下被磨穿。3. In the present invention, the wear resistance of the film layer is very strong. For the sample of 65.4 micron thickness generated in 10 minutes of reaction, compared with the research paper [1] described in the background technology, at 10N load, under the friction condition of 30min, the paper The depth of the wear scar in [1] is about 20 μm, but the depth of the wear scar in the present invention is only about 10 μm. And, the 10min film layer of the present invention can be rubbed with a force of 30N for 30min, and the friction depth is only 20 μm, while the film layer obtained in the low-concentration aluminate in the research paper [1] mentioned in the background technology is under a load of 30N worn out.
④对于厚度为10.3微米左右的薄膜(通过反应2min制得)其耐磨性远高于磷酸盐电解液中制得的相近厚度的膜层。④ For a film with a thickness of about 10.3 microns (made by reacting for 2 minutes), its wear resistance is much higher than that of a film with a similar thickness made in a phosphate electrolyte.
附图说明Description of drawings
图1是锆合金在本发明采用的高浓度铝酸盐电解液、低浓度铝酸盐电解液和铝酸盐电解液中的微弧氧化膜生长速度曲线。Fig. 1 is the micro-arc oxidation film growth rate curve of zirconium alloy in high-concentration aluminate electrolyte, low-concentration aluminate electrolyte and aluminate electrolyte adopted in the present invention.
图2是本发明制备出的铝酸盐电解液中微弧氧化处理2min的氧化膜截面放大5000倍的背散射扫描电镜图像。Fig. 2 is a 5000 times magnified backscattered scanning electron microscope image of the cross section of the oxide film treated by micro-arc oxidation in the aluminate electrolyte prepared by the present invention for 2 minutes.
图3是本发明制备出的铝酸盐电解液中微弧氧化处理2min的氧化膜截面放大18000倍的背散射扫描电镜图像。Fig. 3 is a backscattered scanning electron microscope image enlarged 18000 times of the cross-section of the oxide film treated by micro-arc oxidation in the aluminate electrolyte prepared by the present invention for 2 minutes.
图4是本发明制备出的铝酸盐电解液中微弧氧化处理10min的氧化膜截面放大200倍的背散射扫描电镜图像。Fig. 4 is a backscattered scanning electron microscope image enlarged 200 times of the cross-section of the oxide film treated by micro-arc oxidation in the aluminate electrolyte prepared by the present invention for 10 minutes.
图5是本发明制备出的铝酸盐电解液中微弧氧化处理10min的氧化膜截面放大2000倍的背散射扫描电镜图像。Fig. 5 is a 2000 times enlarged backscattered scanning electron microscope image of the cross-section of the oxide film treated by micro-arc oxidation in the aluminate electrolyte prepared by the present invention for 10 minutes.
图6是采用相同电参数,在低浓度铝酸盐电解液(8g/LNaAlO2+1g/LKOH)中处理30min的氧化膜截面放大1000倍的背散射扫描电镜图像。Fig. 6 is a backscattered scanning electron microscope image magnified 1000 times of the cross-section of the oxide film treated in low concentration aluminate electrolyte solution (8g/LNaAlO 2 +1g/LKOH) for 30min with the same electrical parameters.
图7是采用相同电参数,在磷酸盐电解液中处理20min的氧化膜截面放大20000倍的背散射扫描电镜图像。Figure 7 is a 20,000-fold backscattered scanning electron microscope image of a section of an oxide film treated in a phosphate electrolyte for 20 minutes using the same electrical parameters.
图8是本发明制备出的铝酸盐电解液中微弧氧化处理10min的氧化膜X射线衍射图谱。Fig. 8 is an X-ray diffraction pattern of the oxide film treated by micro-arc oxidation for 10 minutes in the aluminate electrolyte prepared by the present invention.
图9是采用相同电参数,在磷酸盐电解液中处理20min的氧化膜X射线衍射图谱。Fig. 9 is an X-ray diffraction pattern of an oxide film treated in a phosphate electrolyte solution for 20 minutes using the same electrical parameters.
图10是在30N条件下干摩擦30min后的磨痕深度轮廓:(a)本发明制备的高浓度铝酸盐中处理10min、厚度65.4μm的氧化膜(b)低浓度铝酸盐中处理30min、厚度75.8μm的氧化膜。Figure 10 is the wear scar depth profile after dry friction for 30 minutes under 30N conditions: (a) an oxide film with a thickness of 65.4 μm treated in high-concentration aluminate prepared by the present invention for 10 minutes (b) treated in low-concentration aluminate for 30 minutes , Oxide film with a thickness of 75.8 μm.
图11是在10N条件下干摩擦30min后的磨痕深度轮廓:(a)本发明制备的高浓度铝酸盐中处理2min氧化膜(b)磷酸盐处理20min氧化膜。Fig. 11 is the wear scar depth profile after dry rubbing for 30 minutes under 10N conditions: (a) oxide film prepared by the present invention in high-concentration aluminate treated for 2 minutes (b) oxide film treated with phosphate for 20 minutes.
具体实施方式detailed description
下面结合实施例对本发明做进一步的说明。Below in conjunction with embodiment the present invention will be further described.
实施例1:Example 1:
1、锆合金表面快速制备耐磨ZrO2/Al2O3微弧氧化涂层方法,包括:1. Rapid preparation of wear-resistant ZrO 2 /Al 2 O 3 micro-arc oxidation coating method on the surface of zirconium alloy, including:
(1)锆合金表面微弧氧化电解液的制备;(1) Preparation of micro-arc oxidation electrolyte on zirconium alloy surface;
所述电解液的组成是,每1000ml去离子水含:The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO2:32gNaAlO 2 : 32g
KOH:1gKOH: 1g
(2)微弧氧化电源参数的设置:正电流15A/dm2负电流10A/dm2频率:1000Hz(2) Setting of micro-arc oxidation power supply parameters: positive current 15A/dm 2 negative current 10A/dm 2 frequency: 1000Hz
正负占空比:20%Positive and negative duty cycle: 20%
(3)锆合金表面试样的处理:试样尺寸10×20mm,用E-44型环氧树脂密封,待试样固化后,将参与反应的锆合金表面用800-2000#的金相砂纸逐级打磨,然后自来水洗,酒精超声清洗,去离子水洗净。(3) Treatment of the zirconium alloy surface sample: the sample size is 10×20mm, sealed with E-44 epoxy resin, and after the sample is cured, use 800-2000# metallographic sandpaper on the surface of the zirconium alloy participating in the reaction Gradually polished, then washed with tap water, ultrasonically cleaned with alcohol, and cleaned with deionized water.
(4)锆合金表面快速制备耐磨微弧氧化的工艺步骤:将配制好的电解液置于循环水冷却系统下保持温度为20℃,将预处理好的锆合金做阳极,钢板做阴极,设置好微弧氧化电源参数,打开电源,开始试验,达到预定时间(2min-10min,根据需要选择)后,关闭电源,取出锆合金,用去离子水冲洗表面,即得。(4) Process steps for rapid preparation of wear-resistant micro-arc oxidation on the surface of zirconium alloy: place the prepared electrolyte in a circulating water cooling system to keep the temperature at 20°C, use the pretreated zirconium alloy as the anode, and the steel plate as the cathode, Set the parameters of the micro-arc oxidation power supply, turn on the power, start the test, and after the predetermined time (2min-10min, select according to needs), turn off the power, take out the zirconium alloy, rinse the surface with deionized water, and you are ready.
(5)同时在低浓度铝酸盐(8g/LNaAlO2+1g/LKOH)中和磷酸盐中(8g/LNa3PO4+1g/LKOH)采用上面的方法制得微弧氧化膜,进行相关检测,与本发明制得的微弧氧化膜的性能进行比较。(5) Simultaneously in low-concentration aluminate (8g/LNaAlO 2 +1g/LKOH) and in phosphate (8g/LNa 3 PO 4 +1g/LKOH), the above method was used to prepare the micro-arc oxidation film, and the correlation Detect and compare with the performance of the micro-arc oxidation film prepared in the present invention.
2、膜层生长速度:2. Film growth rate:
图1为本发明采用的高浓度铝酸盐(32g/LNaAlO2)、低浓度铝酸(8g/LNaAlO2)以及磷酸盐(8g/LNa3PO4)电解液中微弧氧化膜的生长曲线。从图1中看出,本发明采用的高浓度铝酸盐中微弧氧化膜的生长速度最高。Fig. 1 is the growth curve of the micro-arc oxidation film in the high-concentration aluminate (32g/LNaAlO 2 ), low-concentration aluminate (8g/LNaAlO 2 ) and phosphate (8g/LNa 3 PO 4 ) electrolytes used in the present invention . It can be seen from Fig. 1 that the growth rate of the micro-arc oxidation film in the high-concentration aluminate used in the present invention is the highest.
3、涂层结构与成分分析:3. Coating structure and composition analysis:
当用32g/L铝酸钠电解液,反应为2min时候,膜层结构为一层,膜层结构致密。如图2和图3。When 32g/L sodium aluminate electrolyte is used and the reaction time is 2 minutes, the film structure is one layer and the film structure is dense. Figure 2 and Figure 3.
当用32g/L铝酸钠反应为10min时,涂层为黑色的氧化铝和灰白色的氧化锆混合层(背散射电镜中原子序数低的Al显黑色,而原子序数高的锆为白色),没有大的裂纹与孔洞,与基体结合非常紧密。如图4和图5。对图5中的A点进行元素成分分析,结果为O54.77,Al39.15,Zr6.08(at%),其主要成分是氧化铝。When reacting with 32g/L sodium aluminate for 10 minutes, the coating is a mixed layer of black alumina and off-white zirconia (Al with a low atomic number appears black in the backscattered electron microscope, while zirconium with a high atomic number is white), There are no large cracks and holes, and it is very tightly combined with the matrix. See Figure 4 and Figure 5. The element composition analysis of point A in Fig. 5 shows that the result is O54.77, Al39.15, Zr6.08 (at%), and its main component is alumina.
采用低浓度的电解液时,膜层结构如图6所示,膜层分为内外结构,图6中B点的成分为O58.28,Al5.07,Zr36.35(at.%),其主要成分是氧化锆。我们之前发表文章(背景技术中的研究文献[1])和图6的成分分析结果类似(因为都为低浓度铝酸盐电解液),因此,本发明明显改变了涂层中氧化铝的含量,使其含量大大升高。When using a low-concentration electrolyte, the film layer structure is shown in Figure 6, and the film layer is divided into internal and external structures. The composition of point B in Figure 6 is O58.28, Al5.07, Zr36.35 (at.%), which The main ingredient is zirconia. Our previously published article (research literature [1] in the background technology) and the component analysis result of Fig. 6 are similar (because all are low-concentration aluminate electrolytes), therefore, the present invention has obviously changed the content of aluminum oxide in the coating , to greatly increase its content.
当采用相同电参数,在磷酸盐电解液中处理20min的氧化膜涂层分为内外两层,伴有大量裂纹,如图7所示。When the same electrical parameters are used, the oxide film coating treated in the phosphate electrolyte for 20 minutes is divided into two layers, inner and outer, with a large number of cracks, as shown in Figure 7.
4、相组成分析:4. Phase composition analysis:
本发明中,当用铝酸盐反应生成的膜中,相组成为四方相氧化锆和γ氧化铝,如图8。当采用相同电参数在磷酸盐制备的膜层中,相组成为单斜相氧化锆(m-ZrO2)(图9)。In the present invention, in the film formed by reacting with aluminate, the phase composition is tetragonal zirconia and γ-alumina, as shown in FIG. 8 . When using the same electrical parameters in the film layer prepared by phosphate, the phase composition is monoclinic zirconia (m-ZrO 2 ) ( FIG. 9 ).
5.耐磨性测试:5. Abrasion resistance test:
微弧氧化膜的耐磨性用使用CETRUMT-3摩擦仪,此方法是用直径为9.5mm,硬度为62HRC的Cr钢球在膜层表面进行往复式摩擦,行程为7.2mm,分别使用载荷为10N和30N的力,控制频率为5Hz.并用轮廓仪对磨痕深度及磨痕形貌进行分析。The wear resistance of the micro-arc oxidation film is tested using a CETRUMT-3 tribometer. This method is to use a Cr steel ball with a diameter of 9.5mm and a hardness of 62HRC to perform reciprocating friction on the surface of the film layer. The stroke is 7.2mm, and the load is respectively The force of 10N and 30N, the control frequency is 5Hz. The depth of wear scar and the shape of wear scar are analyzed by profilometer.
(1)本发明和低浓度铝酸盐中得到的膜层耐磨性比较(1) The wear resistance of the film layer obtained in the present invention and low concentration aluminate is compared
将本发明使用的高浓度铝酸钠电解液(32g/LNaAlO2)反应10min,得到的膜层厚度为~65.4μm的膜层(图4,图5)和低浓度的铝酸盐(8g/LNaAlO2+1g/LKOH)中反应30min的膜层(厚度75.8μm,图6)在载荷30N下进行了30min的干摩擦试验,其结果如图10,本发明采用的高浓度铝酸盐中得到的膜层其磨痕深度大约为20μm,而低浓度铝酸盐中制备的膜层的磨痕深度为~114μm(膜层被磨穿)。同样,背景技术中的研究文献[1]中的膜层在30N下也被磨穿。The high-concentration sodium aluminate electrolyte solution (32g/LNaAlO 2 ) used in the present invention was reacted for 10 minutes to obtain a film layer with a thickness of ~65.4 μm (Fig. 4, Fig. 5) and a low-concentration aluminate (8g/L LNaAlO 2 +1g/LKOH) reacted 30min film layer (thickness 75.8μm, Fig. 6) carried out 30min dry friction test under load 30N, its result is shown in Fig. 10, obtained in the high concentration aluminate that the present invention adopts The wear scar depth of the film layer prepared in low concentration aluminate is about 20 μm, while the wear scar depth of the film layer prepared in low concentration aluminate is ~114 μm (the film layer is worn through). Similarly, the film layer in the research document [1] in the background technology is also worn through under 30N.
(2)本发明和磷酸盐电解液中得到的膜层耐磨性比较(2) the film layer abrasion resistance that obtains in the present invention and phosphate electrolyte compares
在本发明使用的浓铝酸钠电解液(32g/LNaAlO2)反应2min,得到的膜层厚度为~10.3μm的膜层(图2,图3)和磷酸盐中反应20min得到的~10μm左右膜层(图7)在载荷10N下进行了30min的干摩擦试验,其结果如图11,本发明采用的高浓度铝酸盐中反应2min的样品经过摩擦后其磨痕深度大约为3μm,而磷酸盐电解液中制备的膜层的磨痕深度为~40μm(膜层被磨穿)。React in the concentrated sodium aluminate electrolyte (32g/LNaAlO 2 ) used in the present invention for 2 minutes, and the obtained film layer thickness is ~10.3 μm (Fig. 2, Fig. 3) and the film layer obtained by reacting in phosphate for 20 minutes to ~10 μm The film layer (Fig. 7) has been subjected to a dry friction test for 30 min under a load of 10 N, and the results are shown in Fig. 11. The wear scar depth of the sample reacted for 2 min in the high-concentration aluminate used in the present invention is about 3 μm after friction, while The wear scar depth of the film prepared in the phosphate electrolyte was ~40 μm (the film was worn through).
本发明采用高浓度铝酸盐电解液快速制备出耐磨ZrO2/Al2O3微弧氧化涂层,膜层生长速度是低浓度铝酸盐中膜层生长速度的2倍左右,相比磷酸盐中得到的膜层,其生长速度提高10倍左右,从而可以大大降低工艺的能耗。而且膜层的耐磨性得到极大程度的提高,使其在核反应堆及其生物应用方面具有更大的使用价值。The invention adopts high-concentration aluminate electrolyte to quickly prepare wear-resistant ZrO 2 /Al 2 O 3 micro-arc oxidation coating, and the growth rate of the film layer is about 2 times that of the film layer in low-concentration aluminate. The growth rate of the film layer obtained in phosphate is increased by about 10 times, which can greatly reduce the energy consumption of the process. Moreover, the wear resistance of the film layer is greatly improved, so that it has greater use value in nuclear reactors and biological applications.
综合所述,本发明的优点是成膜速度快,膜层结构均匀,含有大量氧化铝;膜层耐磨性远远超过一般的锆合金在低浓度铝酸盐和磷酸盐等电解液中得到的微弧氧化膜。In summary, the advantages of the present invention are that the film forming speed is fast, the film layer structure is uniform, and contains a large amount of alumina; micro-arc oxidation film.
实施例2:其余制备和检测步骤同实施例1,只是电解液和参数有所不同:Embodiment 2: The rest of the preparation and detection steps are the same as in Embodiment 1, except that the electrolyte and parameters are different:
(1)锆合金表面微弧氧化电解液的制备;(1) Preparation of micro-arc oxidation electrolyte on zirconium alloy surface;
所述电解液的组成是,每1000ml去离子水含:The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO2:45gNaAlO 2 : 45g
NaOH:5gNaOH: 5g
(2)微弧氧化电源参数的设置:正电流15A/dm2负电流15A/dm2 (2) Setting of micro-arc oxidation power supply parameters: positive current 15A/dm 2 negative current 15A/dm 2
频率:2500HzFrequency: 2500Hz
正负占空比:10%Positive and negative duty cycle: 10%
效果同实施例1,成膜速度快,膜层结构均匀,含有大量氧化铝;膜层耐磨性远远超过一般的锆合金在低浓度铝酸盐和磷酸盐等电解液中得到的微弧氧化膜。The effect is the same as in Example 1, the film forming speed is fast, the film layer structure is uniform, and contains a large amount of alumina; the wear resistance of the film layer far exceeds the micro-arc obtained by ordinary zirconium alloys in low-concentration aluminate and phosphate electrolytes. Oxide film.
实施例3:其余制备和检测步骤同实施例1,只是电解液和参数有所不同:Embodiment 3: The rest of the preparation and detection steps are the same as in Embodiment 1, except that the electrolyte and parameters are different:
(1)锆合金表面微弧氧化电解液的制备;(1) Preparation of micro-arc oxidation electrolyte on zirconium alloy surface;
所述电解液的组成是,每1000ml去离子水含:The composition of described electrolytic solution is, every 1000ml deionized water contains:
NaAlO2:60gNaAlO 2 : 60g
KOH:10gKOH: 10g
(2)微弧氧化电源参数的设置:正电流20A/dm2负电流10A/dm2 (2) Setting of micro-arc oxidation power supply parameters: positive current 20A/dm 2 negative current 10A/dm 2
频率:5000HzFrequency: 5000Hz
正负占空比:30%Positive and negative duty cycle: 30%
效果同实施例1,成膜速度快,膜层结构均匀,含有大量氧化铝;膜层耐磨性远远超过一般的锆合金在低浓度铝酸盐和磷酸盐等电解液中得到的微弧氧化膜。The effect is the same as in Example 1, the film forming speed is fast, the film layer structure is uniform, and contains a large amount of alumina; the wear resistance of the film layer far exceeds the micro-arc obtained by ordinary zirconium alloys in low-concentration aluminate and phosphate electrolytes. Oxide film.
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