Adhesion property of AlCrNbSiTi high-entropy alloy coating on zirconium:experimental and theoretical studies

Experimental scratch tests and first-principles calculations were used to investigate the adhesion property of AlCrNbSiTi high-entropy alloy(HEA)coatings on zirconium substrates.AlCrNbSiTi HEA and Cr coatings were deposited on Zr alloy substrates using multi-arc ion plating technology,and scratch tests were subsequently conducted to estimate the adhesion property of the coatings.The results indicated that Cr coatings had better adhesion strength than HEA coatings,and the HEA coatings showed brittleness.The special quasi-random structure approach was used to build HEA models,and Cr/Zr and HEA/Zr interface models were employed to investigate the cohesion between the coatings and Zr substrate using first-principles calculations.The calculated interface energies showed that the cohesion between the Cr coating and the Zr substrate was stronger than that of the HEA coating with Zr.In contrary to Al or Si in the HEA coating,Cr,Nb,and Ti atoms binded strongly with Zr substrate.Based on the calculated elastic constants,it was found that low Cr and high Al content decreased the mechanical performances of HEA coatings.Finally,this study demonstrated the utilization of a combined approach involving first-principles calculations and experimental studies for future HEA coating development.

First-principles study on the diffusion behavior of Cs and I in Cr coating

Cs and I can migrate through fuel-cladding interfaces and accelerate the cladding corrosion process induced by the fuel-cladding chemical interaction.Cr coating has emerged as an important candidate for mitigating this chemical interaction.In this study,first-principles calculations were employed to investigate the diffusion behavior of Cs and I in the Cr bulk and grain boundaries to reveal the microscopic interaction mitigation mechanisms at the fuel-cladding interface.The interaction between these two fission products and the Cr coating were studied systematically,and the Cs and I temperature-dependent diffusion coefficients in Cr were obtained using Bocquet’s oversized solute-atom model and Le Claire’s nine-frequency model,respectively.The results showed that the Cs and I migration barriers were significantly lower than that of Cr,and the Cs and I diffusion coefficients were more than three orders of magnitude larger than the Cr self-diffusion coefficient within the temperature range of Generation-IV fast reactors(below 1000 K),demonstrating the strong penetration ability of Cs and I.Furthermore,Cs and I are more likely to diffuse along the grain boundary because of the generally low migration barriers,indicating that the grain boundary serves as a fast diffusion channel for Cs and I.

HiPIMS制备Cr/CrCN多层涂层的结构及耐腐蚀性能研究

PVD方法沉积的Cr涂层因耐腐蚀性能较差而难以大规模应用,利用复合多层膜层结构设计能打断贯穿性柱状晶生长,减小孔隙率,提高PVD沉积Cr涂层的耐蚀性。采用高功率脉冲磁控溅射(HiPIMS)耦合同步脉冲偏压技术,在316L不锈钢基体表面沉积Cr/CrCN多层涂层。利用SEM、XRD、EDS和Raman表征了涂层的形貌、组成与组织结构,采用电化学测试、酸性盐雾测试研究了4种不同甲烷流量下(5,15,25,35 sccm)制备的Cr/CrCN多层涂层的耐腐蚀性能。结果表明:引入CrCN中间层有效打断了柱状晶的贯穿性生长,涂层表现出致密平整的表面形貌;4种Cr/CrCN多层涂层均对基体具有较好的保护作用,涂层改性样品相比基体的腐蚀电流密度下降;酸性盐雾腐蚀48 h后,通入甲烷流量为25 sccm的多层涂层表面未出现明显的孔蚀现象,表现出最优异的耐腐蚀性能。HiPIMS制备Cr/CrCN多层涂层能够有效提高316L不锈钢的耐腐蚀性能,可为PVD镀Cr涂层的耐蚀性能优化设计和工业化应用提供参考。

Structure and mechanical properties of thick Cr/Cr_2N/CrN multilayer coating deposited by multi-arc ion plating

A Cr/Cr2N/CrN multilayer coating with a thickness of 24.4 μm was deposited by multi-arc ion plating. The coating was systematically characterized by field emission scanning electron microscopy(FESEM), X-ray photoelectron spectrometry(XPS), energy dispersive spectroscopy(EDS), X-ray diffraction(XRD) and transmission electron microscopy(TEM). Hardness and adhesion were tested by nanoindentation and scratch tester, respectively. The friction properties were investigated by a reciprocating UMT-3MT ball-on-disk tribometer in air and seawater. The results showed that the multilayer coating consisted of three different layers, with Cr,Cr2N and CrN phases, respectively. Compared with CrN single layer coating, the adhesion of the multilayer coating was improved significantly, the hardness of the multilayer coating was(21±2) GPa. The corrosion resistance of the multilayer coating was also improved in artificial seawater. The friction coefficient of multilayer coating was lower than that of CrN single layer coating both in air and seawater.

Microstructure and indentation toughness of Cr/CrN multilayer coatings by arc ion plating

Cr/CrN multilayer coatings with bilayer periods in the range from 1351 to 260 nm were prepared on 304 stainless steel substrates by arc ion plating to study the microstructure and properties of multilayer coatings and stimulate their application.SEM results confirm the clear periodicity of the Cr/CrN multilayer coatings and the clear interface between individual layers.XRD patterns reveal that these multilayer coatings contain Cr,CrN and Cr_2N phases.Because Cr layer is softer than its nitride layer,the hardness decreases with the shortening of the bilayer period(or increasing volume fraction of Cr layer).The Cr/CrN multilayer coating with 862 nm period possesses the highest indentation toughness due to a proper individual Cr and nitride layer thickness.However,for the Cr/CrN multilayer with the bilayer period of 1351 nm,it possesses the lowest toughness due to more nitride phase.The indentation toughness of Cr/CrN multilayer coatings is related with their bilayer period.A coating with a proper individual Cr and nitride layer thickness possesses the highest indentation toughness.

锆合金包壳Cr涂层界面元素扩散行为研究进展

随着核反应堆向高燃耗和更长服役寿命方向发展,对包壳材料的安全可靠性提出了更高的要求。锆合金表面Cr涂层由于其优异的抗高温氧化性能、耐腐蚀性能以及与基体良好的兼容性,被认为是最有前景的耐事故涂层包壳材料。综述了近年来涂层Cr与基体Zr界面元素扩散行为的研究成果,重点介绍了Cr涂层不同状态下的界面结构及演变规律,包括沉积、退火、辐照、氧化等状态。总结了Cr的扩散、分布和金属间化合物Zr-Cr-(Fe)层的生长动力学模型,归纳了界面扩散对涂层结构及性能的不利影响。扩散阻挡层是一种抑制涂层与基体互扩散的有效结构,介绍了阻挡层设计制备原则以及现有的和潜在的金属或陶瓷阻挡层材料,分析了2类典型阻挡层的优缺点。金属阻挡层能抑制Cr的扩散并延迟Cr-Zr共晶反应,但需要考虑中子经济性;虽然陶瓷阻挡层阻隔元素扩散的性能优异,但由于其与锆合金力学性能和热膨胀系数的差异明显,易产生微裂纹,需要考虑其抗裂性。最后提出了采用实验与分子动力学等相结合的多尺度研究方法开展界面研究,同时指出了目前研究工作中亟待解决的关键问题,这为后续的锆合金表面耐事故涂层研究与开发提供了重要参考。

STUDY ON PTA CLAD (Cr,Fe)_7C_3/γ-Fe CERAMAL COMPOSITE COATING

A wear resistant （Cr, Fe）7C3/γ-Fe ceramalcomposite coating wasfabricatedon substrate of a 0.45% C carbon steel by plasma transferred arc （PTA） cladding process using the Fe-Cr-C elemental powder blends. The microstructure, microhardness and dry sliding wear resistance of the coating were evaluated. Results indicate that the plasma transferred arc clad ceramal composite coating has a rapidly solidified microstructure consisting of blocky primary （Cr, Fe）7C3 and the interblocky （ Cr, Fe）7C3/γ-Fe eutectics and is metallurgically bonded to the 0.45%C carbon steel substrate. The ceramal composite coating has high hardness and excellent wear resistance under dry sliding wear test condition.

PTA clad (Cr,Fe)_7C_3/γ-Fe in situ ceramal composite coating

A wear-resistant （Cr, Fe）7C3/γ-Fe in situ ceramal composite coating was fabricated on the substrate of 0.45wt%C carbon steel by a plasma-transferred arc cladding process using the Fe-Cr-C elemental powder blends. The microstructure, microhardness, and dry-sliding wear resistance of the coating were evaluated. The results indicate that the microstructure of the coating, which was composed of （Cr, Fe）7C3 primary phase uniformly distributed in the γ-Fe, and the （Cr, Fe）7C3 eutectic matrix was metallurgically bonded to the 0.45wt%C carbon steel substrate. From substrate to coating, the microstructure of the coating exhibited an evident epitaxial growth character. The coating, indehiscent and tack-free, had high hardness and appropriate gradient. It had excellent wear resistance under the dry sliding wear test condition.

Cr涂层对Zr-4合金蠕变行为的影响

报道化学气相沉积Cr涂层对Zr-4合金蠕变性能的影响以及Cr涂层在服役温度下的热稳定性。利用扫描电镜、电子探针显微分析和电子背散射衍射研究样品的显微组织。结果表明:样品Zr-4基体中晶粒呈等轴状,存在明显的<0001>//ND织构。蠕变后涂层样品的Zr-4合金基体中亚晶界数量明显低于无涂层样品Zr-4合金基体中亚晶界数量,表明Cr涂层显著降低了Zr-4合金基体在蠕变过程中承载的应力,提高了合金的抗蠕变性能。Cr涂层在长时间扩散实验中保持高稳定性。涂层在高蠕变应力下(350℃时不小于157 MPa,400℃时不小于137 MPa)出现裂纹。系统总结蠕变断裂的数据,得到了关于稳态蠕变速率与蠕变断裂时间的Monkman-Grant关系式。

Effects of Cr interlayer on mechanical and tribological properties of Cr-Al-Si-N nanocomposite coating

Cr-A1-Si-N coatings were deposited on SUS 304 substrate by a hybrid coating system. A Cr interlayer was introduced between Cr-A1-Si-N coating and SUS 304 substrate to improve the coating adherence. The effects of Cr interlayer on the microhardness, adhesion, and tribological behavior of Cr-A1-Si-N coatings were systematically investigated. The results indicate that the microhardness of the Cr-A1-Si-N coatings gradually deceases with increasing thickness of Cr interlayers. The adhesion between Cr-A1-Si-N and SUS 304 substrate is improved by addition of the Cr interlayers. A peak critical load of-50 N is observed for the coating containing Cr interlayer of 60 nm as compared - 20 N for the coating without Cr interlayer. The thicker Cr interlayers result in reduced critical load values. Moreover, the wear resistance of the Cr-AI-Si-N coatings is greatly enhanced by introducing the Cr interlayer with thickness of 60 nm in spite of the decreased microhardness. The friction coefficient of the coating system is also moderately reduced.

Pt改性梯度NiCrAlY涂层的热腐蚀行为研究

为了进一步提高NiCrAlY涂层的抗热腐蚀性能,利用电弧离子镀技术在DZ125合金表面分别沉积NiCrAlY/NiAl/Al涂层(coating A)、NiCrAlY/Pt/NiAl/Al涂层(coating B),再经真空扩散退火处理形成成分渐变的梯度涂层结构。在涂层中引入改性元素Pt以改善涂层的抗热腐蚀能力,对比研究了2种涂层体系在900℃不同混合盐中的热腐蚀行为;利用SEM、EDS、XRD以及EPMA分析了涂层经过热腐蚀后的微观形貌、物相组成和元素分布。结果表明:在900℃的K_(2)SO_(4)+Na_(2)SO_(4)混合盐中,coating A表面的氧化膜发生了大面积的剥落,coating B中的Pt抑制了S在涂层/氧化膜界面处的偏析,增强了氧化膜的黏附性。在900℃的NaCl+Na_(2)SO_(4)混合盐中,coating A的Cr元素和O元素分别发生了外扩散和内扩散,Cr外扩散易与S反应生成有害相Cr_(x)S_(y)。coating B中的Pt抑制了Cr、O元素的外扩散和内扩散。在NiCrAlY层和NiAl层之间增加Pt层,显著提升了NiCrAlY涂层在混合盐中的抗热腐蚀能力。

Wear resistance of Zr/WC composite coatings on Cr12MoV steel surface by electric spark deposition

Zr/WC composite coating was prepared on the surface of Cr12MoV steel by electric spark deposition technology to change its surface properties. The surface and worn surface morphology of the coating were observed using scanning electron microscope. Dry friction and wear tests of the coatings were carried out at room temperature. The results show that the coating is continuous and uniform, and the thickness was about 50-60 μm. The microhardness of the coating surface was highest at 1140 HV_(200g), which was significantly higher than that of the substrate. The ear tests results show that the wear weight loss, wear volume and wear rate follow the following rules: Cr12MoV>WC coating> Zr/WC composite coating.

Ultrasonic characterization of modified Cr_2O_3 coatings by reflection coefficient spectroscopy

Pores,microcracks and density of plasma sprayed Cr2O3 coatings before and after high-intensity pulsed ion beam(HIPIB) irradiation were investigated using the ultrasonic reflection coefficient spectroscopy(URCS).The URCS was analyzed based on an acoustic transmission model for the multi-layered structure.The longitudinal velocity in the coatings was calculated from the experimental URCS,and the attenuation coefficient expression was deduced by comparing the experimental and numerical fitting amplitude spectral lines.The longitudinal velocity of as-sprayed Cr2O3 coating is 2 002 m/s,and increases to 2 099 and 2 148 m/s after being irradiated by HIPIB with 1 and 5 shots.Correspondingly,the factor A changes from 0.046 to 0.026 and 0.020 and n from 1.702 to 1.658 and 1.649 in the attenuation coefficient expression of α=Af n.It is observed that the surface morphology of Cr2O3 coatings changes from rough and porous to smooth and uniform with the increase of shot number,which accords with the ultrasonic analyses reasonably.The URCS seems to provide a convenient and nondestructive method to characterize surface modification of the plasma sprayed coatings.

Structure and cavitation erosion behavior of HVOF sprayed multi-dimensional WC-10Co4Cr coating

A new kind of multi-dimensional WC-10Co4Cr coating which is composed of nano,submicron,micron WC grains and CoCr alloy,was developed by high velocity oxy-fuel(HVOF)spraying.Porosity,microhardness,fracture toughness and cavitation erosion resistance of the multi-dimensional coating were investigated in comparison with the bimodal and nanostructured WC?10Co4Cr coatings.Moreover,the cavitation erosion behavior and mechanism of the multi-dimensional coating were explored.Results show that HVOF sprayed multi-dimensional WC-10Co4Cr coating possesses low porosity(≤0.32%)and high fracture toughness without obvious nano WC decarburization during spraying.Furthermore,it is discovered that the multi-dimensional WC-10Co4Cr coating exhibits the best cavitation erosion resistance which is enhanced by approximately 28%and 34%,respectively,compared with the nanostructured and bimodal coatings in fresh water.The superior cavitation resistance of multi-dimensional WC-10Co4Cr coating may originate from the unique micro?nano structure and excellent properties,which can effectively obstruct the formation and propagation of cavitation erosion cracks.

电弧离子镀Al-Cr-O/Zr-O+NiCoCrAlSiY和Al-Cr-O+NiCoCrAlSiY涂层的抗氧化性和隔热性能

采用电弧离子镀在高温合金表面沉积Al-Cr-O/Zr-O多层涂层和Al-Cr-O单层涂层+NiCoCrAlSiY结合层,并在1000~1200℃下进行热处理。利用扫描电子显微镜和X射线衍射仪分析涂层的显微组织和物相结构。结果表明,Al-Cr-O/Zr-O多层涂层和Al-Cr-O单层涂层均呈现出致密的球形结构。热处理后,Al-Cr-O/Zr-O涂层表面出现裂纹,且裂纹随着温度的升高而增多和变粗。然而,Al-Cr-O涂层经热处理后其表面胞状结构转变为紧密连接的粒状结构,并且随着热处理温度的升高,粒状结构显著长大。由于作为氧离子导体以及t-ZrO_(2)的致密度低于α-Al_(2)O_(3),Al-Cr-O/Zr-O涂层中的t-ZrO_(2)为氧离子向涂层内扩散提供了通道,因此,Al-Cr-O单层涂层+NiCoCrAlSiY涂层体系的高温抗氧化性优于Al-Cr-O/Zr-O多层涂层+NiCoCrAlSiY涂层体系。但是,由于更大的陶瓷涂层厚度,t-ZrO_(2)相的低热导率以及层间界面的热反射作用,Al-Cr-O/Zr-O多层涂层+NiCoCrAlSiY涂层体系的隔热性能优于Al-Cr-O单层涂层+NiCoCrAlSiY涂层体系。

INFLUENCE OF PHASE COMPOSITION ON PITTING CORROSION RESISTANCE OF SPUTTERED COATING OF 1Cr18Ni9Ti STAINLESS STEEL

A series of single bcc,bcc plus fcc duplex and single fcc microcrystalline coatings of 1Cr18Ni9Ti stainless steel were prepared by using sputtering technique.The resistance against pitting corrosion was studied by measurements of pitting corrosion potentials and electrochemical noise during initiation of corrosion pits.The results show that the sputtered coatings with single bcc phase or single fcc structure are more resistant to pitting corrosion than those with bcc plus fcc duplex phase structure.

Sliding wear behaviors of electrodeposited Ni composite coatings containing micrometer and nanometer Cr particles

Micrometer and nanometer Cr particles were co-deposited with Ni by electroplating from a nickel sulfate bath containing a certain content of Cr particles. Cr microparticles are in a size range of 1-5 μm and Cr nanoparticles have an average size of 40 nm. The friction and the wear performance of the co-deposited Ni-Cr composite coatings were comparatively evaluated by sliding against Si3N4 ceramic balls under non-lubricated conditions. It is found that the incorporation of Cr particles enhances the microhardness and wear resistance of Ni coatings. The wear resistance of Ni composite coating containing Cr nanoparticles is higher than that of the Ni composite coating containing Cr microparticles with a comparable Cr particle content. The co-deposition of smaller nanometer Cr particles with Ni effectively reduces the size of Ni crystals and significantly increases the hardness of the composite coatings due to grain-refinement strengthening and dispersion-strengthening,resulting in a significant improvement of wear resistance of the Ni-Cr nanocomposite coatings.

Improvement on the Oxidation Resistance of a Ti_3Al Based Alloy by Cr1-xAl_xN (0≤x≤0.47) Coatings

Cr1-xAlxN coatings have been deposited on a Ti3Al based alloy by reactive sputtering method. The results of the isothermal oxidation test at 800-900℃ showed that Cr1-xAlxN coatings could remarkably reduce the oxidation rate of the alloy owing to the formation of Al2O3＋Cr2O3 mixture oxide scale on the surface of the coatings. No spallation of the coatings or oxide scales took place during the cyclic oxidation at 800℃. Ti was observed to diffuse into the coatings, the diffusion distance of which was very short, and the diffusion ability of it was proportional to the AI content in the coatings. Compared to Ti, Nb can diffuse much more easily through the whole coatings and oxide scales.

Structure of Micro-nano WC-10Co4Cr Coating and Cavitation Erosion Resistance in NaCl Solution

Cavitation erosion （CE） is the predominant cause for the failure of overflow components in fluid machinery. Advanced coatings have provided an effective solution to cavitation erosion due to the rapid development of surface engineering techniques. However, the influence of coating structures on CE resistance has not been sys- tematically studied. To better understand their relationship, micro-nano and conventional WC-10Co4Cr cermet coat- ings are deposited by high velocity oxygen fuel spray- ing（HVOF）, and their microstructures are analyzed by OM, SEM and XRD. Meanwhile, characterizations of mechan- ical and electrochemical properties of the coatings are carried out, as well as the coatings＇ resistance to CE in 3.5 wt % NaC1 solution, and the cavitation mechanisms are explored. Results show that micro-nano WC-10Co4Cr coating possesses dense microstructure, excellent mechanical and electrochemical properties, with very low porosity of 0.26 4-0.07% and extraordinary fracture toughness of 5.58 4-0.51 MPa.m1/2. Moreover, the CE resistance of micro-nano coating is enhanced above 50% than conventional coating at the steady CE period in 3.5 wt % NaC1 solution. The superior CE resistance of micro- nano WC-10Co4Cr coating may originate from the unique micro-nano structure and properties, which can effectively obstruct the formation and propagation of CE crack. Thus,a new method is proposed to enhance the CE resistance of WC-10Co4Cr coating by manipulating the microstructure.

Preparation Technology and Performances of Zn-Cr Coating on Sintered NdFeB Permanent Magnet

Zn-Cr coating was prepared on the surface of sintered NdFeB permanent magnet samples and preparation parameters were established. The anticorrosive property of Zn-Cr coating on NdFeB was studied by whole-immersion test in NaCl solution and compared with that of zinc plating and nickel plating on NdFeB. Open-circuit potential and self-corrosion current of NdFeB samples with and without Zn-Cr coating were measured. The micro-morphology and composition of Zn-Cr coming were analyzed through SEM, XPS, EDS and XRD. The effect of Zn-Cr coating on magnetic property of NdFeB magnet was also investigated. It is exposed that Zn-Cr coating is anodic type coating for NdFeB magnet, and provided substrate electrochemical protection, barrier protection and passivation protection. The anticorrosion property of NdFeB magnet is obviously enhanced by Zn-Cr coating while the magnet property of NdFeB magnet changed little.