Preparation of chromium oxynitride and chromium nitride films by DC reactive magnetron sputtering and their material properties

Abstract

Thin films of ～2 μm thick chromium nitride (CrN) were prepared by direct current (dc) reactive magnetron sputter deposition on steel substrates. XPS spectra showed the presence of chromium in the form of CrN with traces of Cr₂O₃ on CrN thin films. XRD spectrum shows CrN peaks at 37 and 43° which corresponds to (111) and (200) planes. Surface topography from atomic force microscope shows that films have continuous coverage of rectangular cell like patterns. Corrosion performance of these films on low carbon steel substrates in 3·5%NaCl solution was evaluated using electrochemical techniques. A less negative value of E_corr and lower value of I_corr signify an improvement in corrosion resistance of the CrON coating. Scanning vibrating electrode technique (SVET) was able to discretely map relative cathodic and relative anodic sites at a macroscopic defect and to record the changes of local electrode activities in a real time.     

等离子体辉光放电制备W-Mo共渗层在还原性酸中耐蚀性研究

在β相变点以下,通过空心阴极等离子体辉光放电技术,在Ti6Al4V合金表面形成W-Mo共渗层来提高钛合金基体在还原性酸中的耐蚀性。分别利用扫描电子显微镜、能谱仪和X射线衍射仪对试样的表面形貌、成分分布和相组成进行分析。结果显示在Ti6Al4V合金表面形成一层约23μm厚,由AlMoTi2 和 TixW1-x物相组成的共渗层。利用电化学工作站,在常温静态条件下,对试样在还原性酸(硫酸和盐酸)中进行耐蚀性研究。结果表明,经过共渗处理的试样在还原性酸中,能保持稳定的腐蚀电位并且其腐蚀电流密度仅为原始试样的1/10 和 1/6。此外,相较于钛合金基体,处理后的试样表面没有发现腐蚀产物和裂纹,表明没有腐蚀脱落现象发生。因此,在保证基体基本性能的前提下,钛合金试样的耐蚀性能明显提高。     

Effect of plasma nitriding of electroplated chromium coatings on the corrosion protection C45 mild steel

Plasma nitriding is a promising posttreatment technique to create a nitride layer on electroplated chromium coatings for improving their corrosion resistance. In the present study, the effects of plasma nitriding on the corrosion properties of electroplated chromium/C45 mild steel were investigated using electrochemical characterization. The chromium plated samples were nitrided using a pulsed direct current glow discharge in an NH₃ atmosphere. The polarization curve measurement results showed that the plasma nitrided samples exhibited more positive corrosion potentials (E_corr), smaller corrosion currents (I_corr), and evident passivation when compared with unnitrided chromium plating/substrate system. The high value of E_corr and low value of I_corr imply an improvement of the corrosion resistance of the coating/substrate system after plasma nitriding.     

Corrosion behavior of martensitic and precipitation hardening stainless steels treated by plasma nitriding

Plasma nitriding is a well established technology to improve wear and corrosion properties of austenitic stainless steels. Nevertheless, in the case of martensitic stainless steels, it continues being a problem mainly from the corrosion resistance viewpoint.In this work, three high chromium stainless steels (M340, N695 and Corrax) were hardened by ion nitriding at low temperature, intending to preserve their corrosion resistance.Corrosion behavior was evaluated by CuSO₄ spot, salt spray fog and potentiodynamic polarization in NaCl solution. Microstructure was analyzed by optical microscopy, SEM (EDS) and glancing angle X-ray diffraction. All the samples showed an acceptable corrosion resistance in experiments with CuSO₄, but in salt spray fog and electrochemical tests, only Corrax showed good behavior. The poor corrosion performance could be explained by chromium carbides formed in thermal treatment stage in martensitic steels and chromium nitrides formed during nitriding, even though the process was carried out at low temperature.     

Silicon nitride and oxynitride films deposited from organosilicon plasmas: ToF-SIMS characterization with multivariate analysis

In this work bis(dimethylamino)dimethylsilane (BDMADMS) has been utilized as precursor for plasma enhanced chemical vapour deposition (PECVD) of silicon nitride-like and silicon oxynitride-like thin films. The effect of input power and O₂/BDMADMS ratio on the film surface chemistry has been investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and principal component analysis (PCA). Changes in surface composition have been correlated to infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses. The results show that the PCs profile obtained by increasing input power during the deposition is correlated to the transition from an organic to an inorganic silicon nitride-like coating while at high input power, if the oxygen concentration in the feed is increased, the following transition occurs: inorganic silicon nitride-like → oxynitride-like → oxide-like.     

Plasma nitriding of austenitic stainless steel in N2 and N2-H2 dc pulsed discharge

AISI 302/304 austenitic stainless steels have been nitrided in N₂ and N₂-H₂ glow discharge plasmas powered by a high frequency dc pulsed power supply. In a pure nitrogen plasma, no increase in surface hardness from the initial value has been observed. In a N₂-H₂ gas admixture, a 3-4 times increase in hardness has been found, which confirms the necessity of hydrogen gas as a powerful reagent. Grazing incidence X-ray diffraction (GIXRD) shows the presence of three phases of nitride (Fe₃N, Fe₄N and CrN) along with iron oxide (Fe₂O₃). It is found in a N₂ plasma at a sample temperature of 540 °C that at 200 kHz, maximum peak intensity of iron oxide/nitride decreases. In N₂-H₂ plasma treated sample the nitride peak intensity increased in comparison to the intensity in sample nitrided in N₂ plasma. Optical emission spectroscopy (OES) has been used to investigate the active species present during nitriding in the near-cathode region. Emission bands of neutral and ionic molecular species and ionic atomic species of nitrogen have been detected in a nitrogen plasma. In a N₂-H₂ gas admixture, the H_α and H_β lines of Balmer series in addition have been observed. At 20% H₂ addition in nitrogen plasma, a few vibrational state intensities of N₂ and N₂⁺ are observed to be optimized.     

利用双层辉光放电形成Mo-N硬质镀层

用双层辉光放电在钛合金Ti6Al4V表面形成了Mo-N硬质镀层。用X射线衍射仪和纳米压入仪分别对镀层的相结构、硬度和弹性模量进行了研究，并用涂层压入仪对镀层与基体间的结合强度进行了测定。结果表明：Ti6Al4V表面形成了均匀的Mo—N硬质镀层，镀层厚约10μm，由面心立方结构Mo2N化合物构成；Mo2N硬质镀层的硬度和弹性模量分别为13．80GPa和261．65GPa;镀层与基体间具有较好的结合强度。     

Corrosion and mechanical properties of duplex-treated 301 stainless steel

Plasma nitriding is a widely used technique for increasing the surface hardness of stainless steels, and consequently, for improving their tribological properties. It is also used to create an interface between soft stainless steel substrates and hard coatings to improve adhesion. This paper reports on the mechanical and corrosion properties of AISI301 stainless steel (SS) after a duplex treatment consisting of plasma nitriding followed by deposition of Cr bond coat and CrSiN top layer by magnetron sputtering. Mechanical properties of the deposited films, such as hardness (H) and reduced Young's modulus (E_r), were measured using depth-sensing indentation. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were carried out to evaluate resistance to localized and to general corrosion, respectively. The corrosion behavior has been correlated with the microstructure and composition of the surface layers, determined by complementary characterization techniques, including XRD, SEM, and EDS. The CrSiN layers exhibited an H value of 24 GPa, whereas the nitrided layer was shown to present a gradual increase of H from 5 GPa (in the nitrogen-free SS matrix) to almost 14 GPa at the surface. The electrochemical measurements showed that the nitriding temperature is a critical parameter for defining the corrosion properties of the duplex-treated SS. At a relatively high temperature (723 K), the nitrided layer exhibited poor corrosion resistance due to the precipitation of chromium nitride compounds and the depletion of Cr in the iron matrix. This, in turn, leads to poor corrosion performance of the duplex-treated SS since pores and defects in the CrSiN film were potential sites for pitting. At relatively low nitriding temperature (573 K), the nitrided interface exhibited excellent corrosion resistance due to the formation of a compound-free diffusion layer. This is found to favor passivation of the material at the electrode/electrolyte interface of the duplex-treated SS.     

Deposition and characteristics of chromium nitride thin film coatings on precision balls for tribological applications

Thin film hard coatings on rolling element surfaces can enhance the overall wear resistance of rolling element bearings, as demonstrated previously for coated tapered, cylindrical, and spherical roller bearings. Hard coatings in ball bearings are less common because of the difficulty in achieving uniform film thickness on a ball surface. This limitation is overcome by a new process for depositing chromium nitride coatings with uniform thickness on precision balls using ion beam assisted deposition (IBAD) e-beam evaporation. Scanning electron microscopy indicated that the deposited films were smooth and conformal on the ball surfaces with no areas of localized delamination. Auger electron spectroscopy confirmed that Cr₂N and CrN bulk film stoichiometry was achievable by modulating the argon to nitrogen process gas ratio during deposition. Transmission electron microscopy revealed dense, polycrystalline film structure. Film hardness and elastic modulus as measured using nanoindentation on the coated balls met expectations for chromium nitride, and tribological testing of the coated balls in angular contact ball bearings under moderate contact stress levels demonstrated adequate film adhesion for practical use of these coatings in bearing applications.     

H13钢表面镀铬和气体渗氮复合处理的组织及性能

对调质后的H13钢进行镀铬+540 ℃气体渗氮处理,获得氮化铬表层,然后将其进行耐磨试验,并与同温度经常规气体渗氮及离子渗氮后的H13钢试样进行组织及耐磨性对比。结果表明:3种工艺处理后试样的主要磨损机制为粘着磨损和磨粒磨损,镀铬/渗氮试样表面摩擦因数最低,为0.44,耐磨性最好,但镀铬+渗氮层与基体的结合力最差。     

Effect of electrodeposition conditions on the composition, microstructure, and corrosion resistance of Zn-Ni alloy coatings

The formation, composition, and structure of electrodeposited zinc-nickel alloys were investigated. It has been shown that both anomalous and normal codeposition of zinc and nickel can be realized by changing the bath composition and deposition conditions, with the nickel content in the resultant deposit being varied in a wide range (from 2 to 90 at.%). It has been also shown that the ammonical diphosphate electrolyte allows deposition of Zn-Ni coatings with a homogeneous phase structure (Ni₅Zn₂₁ and Ni₃Zn₂₂ intermetallides, a solid solution of Zn in Ni, or a solid solution of Ni in Ni₅Zn₂₁), whereas the weak acid chloride electrolyte produces two-phase coatings consisting of Ni₅Zn₂₁ with the admixture of polycrystalline Zn or Ni. The Zn-Ni coating with a nickel content of 19 at.% consisting of Ni₅Zn₂₁ intermetallic phase exhibits the highest corrosion resistance.     

Microstructure of the composite oxynitrided chromium layers produced on steel by a duplex method

The paper describes the microstructure of the composite layers produced on chromium pre-coated AISI 1045 steel by oxynitriding under glow discharge conditions (duplex method). The layers were examined by the cross-section method using transmission electron microscopy. Their microstructure was composed of the 4 zones: a near-surface CrN-Cr₂O₃ mixture zone about 1 μm thick, a Cr₂N zone about 4 μm thick, a chromium zone-the thickest-about 50 μm, and the thinnest (Cr,Fe)₇C₃ zone about 0.5 μm thick. Cr₂O₃ also occurred in the form of nano-crystalline aggregates, about 1 μm in size, situated in the upper part of the Cr₂N zone. All the zones had a fine-grained structure, except the finest nano-crystalline zone situated at the surface. It was found that, during oxynitriding, the cracks present in the chromium coating are filled up by chromium nitrides and oxides. This may explain the observed improvement of the corrosion resistance.     

Ti基与Cr基氮化物涂层的抗氧化性能

选用TiN,TiAlN,CrN和CrAlN 4种涂层材料,使用电阻炉对试样加热并保温,进行抗氧化性能实验,利用SEM、EDS和XRD获得了氧化结果。结果表明:Ti基涂层的氧化机制以O原子向涂层内部扩散为主;Cr基涂层的抗氧化机制为N原子和Cr离子向涂层表面的扩散所形成的微孔诱发的氧化;Cr基涂层比Ti基涂层具有较好的抗氧化性;Al的加入使得TiAlN与CrAlN涂层的氧化性能和高温后硬度提高,特别是CrAlN氧化后生成的致密Cr2O3和Al2O3混合氧化物使其抗氧化性能达到最优;氧化及涂层与基体的热涨失配使得几类涂层最终开裂失效;四种涂层的抗氧化能力为CrAlN>TiAlN>CrN>TiN。     

Characterization of the surface layers formed on titanium by plasma electrolytic oxidation

This paper is concerned with the surface modification of titanium by the PEO method (plasma electrolytic oxidation) in the solutions which contain Ca, P, Si and Na. The chemical composition of the thus formed surface layers was examined by XPS and EDS. The morphology of the surface was observed by SEM. The phase composition was determined by X-ray diffraction (XRD). The adhesive strength of the oxide layers was evaluated by the scratch-test. The corrosion resistance was determined in a simulated body fluid (SBF) at a temperature of 37 °C by electrochemical methods for various exposure times.The oxide layers obtained were porous and enriched with Ca, P, Si and Na and their properties depended on the electrolyte solution and the parameters of the oxidation process. The results of the electrochemical examinations show that the surface modification by PEO does not worsen the corrosion resistance of titanium after a 13 h exposure in SBF. The electrochemical impedance spectroscopy (EIS) results indicate that the surface layers have a complex structure and that their electric properties undergo changes during long-term exposures in SBF.     

纯钛表面辉光放电W-Mo共渗层的耐磨及耐蚀性能

采用等电位空心阴极辉光放电技术对纯钛进行W-Mo二元共渗,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)、显微硬度计对试样的结构形貌、渗层成分分布及相组成、硬度进行研究.利用摩擦磨损试验仪对试样的摩擦学性能进行研究,利用电化学腐蚀工作站,研究了W-Mo合金渗层在常温静态条件下,在3.5％ NaCl腐蚀介质中的耐蚀性能.结果表明,经W-Mo共渗处理后纯钛表面形成了一层均匀致密的W-Mo改性层,渗层最大厚度达到16.6 μm,最大硬度达到1196HV0.1,是基体的6.85倍.W-Mo共渗后改性层主要由W、Mo、MoTi、TixW1-x相组成.由于表面硬度的大幅提升,试样表面的耐磨性也显著提高,最低摩擦系数仅为0.23,较原始试样的0.516明显减小.测得的试样最低腐蚀速率为0.0016 mm/a,是原始试样的1/230,耐蚀性能也显著提高.     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

Corrosion properties of micro- and nanocomposite copper matrix coatings produced from a copper pyrophosphate bath under pulse current

The aim of this work was the deposition of copper matrix composites under direct and pulse current at different frequencies and the evaluation of their protective properties, in the frame of the research domain of the production of metal matrix composite coatings.The deposits were produced using copper pyrophosphate bath in which 20 g/l of either micro- (mean diameter 2 μm) or nano- (mean diameter 45 nm) SiC particles have been added. A squared current waveform was used with the frequencies 0.01, 0.1, 1, and 10 Hz for the pulse current deposition.The microstructure of all deposits, both on the top surface and in cross section, was studied by Scanning Electron Microscopy. The SiC content was evaluated by EDXs in the case of the micro-composite deposits and by Glow Discharge Optical Emission Spectroscopy for the nanocomposite ones. The protective properties were examined by potentiodynamic measurements in different corrosive environments and by salt spray exposure combined with Electrochemical Impedance Spectroscopy measurements.Both the nanoparticles incorporation and the use of pulse current lead to a noticeable grain refinement and thus to a corrosion resistance increase. The nanocomposite deposits present the highest resistance to both uniform and localized corrosion, strongly correlated to their compact structure. The micro-composite deposits produced under direct current present gaps between the particles and the copper matrix, which lower the corrosion resistance. The use of the pulse current managed to partially close these gaps and increase the corrosion resistance to values similar to those of the pure copper deposits.     

贫铀表面激光氮化层的结构和氧化动力学研究

为了研究激光氮化对金属铀表面结构和性质的影响,利用X射线衍射结合原位高温反应器,研究了不同激光氮化工艺后的贫铀表面结构,并对不同温度下UN的氧化过程进行了原位XRD实验分析,获得了相应条件下的氧化动力学曲线。结果显示,激光扫描速率对贫铀表面氮化层的相结构有显著影响,较快的扫描速率能够获得单一的UN结构,较慢的扫描速率将获得UN和U_2N_3的双相混合层。氧化动力学实验表明,表面激光氮化制备的UN层对基材有很好的保护作用,能够显著降低金属铀的氧化腐蚀速率。较低的温度下UN层的氧化非常缓慢,温度升至180℃以上时氧化速率明显加快,其氧化动力学曲线与贫铀有明显差异,文中对此现象和氮化层的氧化机制进行了分析和讨论。     

Corrosion and tribological behaviors of chromium oxide coatings prepared by the glow-discharge plasma technique

In order to improve the corrosion and tribological properties of steel, chromium oxide coatings were prepared by a new combined process, namely, chromizing and plasma oxidizing treatments using double glow plasma technology under various oxygen flow rates. The composition and microstructure of the coatings were analyzed respectively by means of X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results indicated that the oxygen flow rates had a great effect on the surface structure of the prepared Cr₂O₃ coatings, and dense and smooth Cr₂O₃ coatings were prepared at the oxygen flow rate of 10 sccm. The Cr₂O₃ coatings exhibited the better corrosion resistance which was in good agreement with the results obtained by the microstructure studied. Further mechanical properties test showed that the Cr₂O₃ coatings with high hardness and elastic modulus adhered well to the steel substrates and displayed excellent wear resistance and low coefficient of friction under dry sliding wear test conditions. The wear mechanism was mostly dominated by the “soft abrasion”.     

混合法在AZ91D镁合金表面制备的扩散氮化钛涂层的结构及性能

采用钛涂层物理气相沉积法（PVD）和渗氮法结合的混合方法在AZ91D镁合金表面制备扩散氮化钛涂层。涂层由含Ti的氮化物和氧化物的薄的表层区,钛中间区和Ti-Al-Mg型扩散区组成。因涂层改善了合金的耐蚀性能,在铝基亚层上通过氮氧共渗制备涂层时,合金能够得到最好的耐蚀性能。