Cover Picture: Materials and Corrosion. 4/2020

Cover: Hydrolysis of anionic polyacrylamide (HPAM) adsorbs on the surface of metal to form a network of protective fi lm. The corrosion scales of N80 steel includes an inner film which is composed of FeCO₃ and an outer film composed of FeS₂ in HPAM/H₂S/CO₂ environment. More detailed information can be found in: Baojun Dong, Dezhi Zeng, Zhiming Yu, Haixin Zhang, Huiyong Yu, Gang Tian, Yonggang Yi, Role of polyacrylamide concentration on Corrosion Behavior of N80 steel in the HPAM/H₂S/CO₂ environment, Materials and Corrosion 2020 , 71, 526.     

Environmental factors affecting the corrosion behaviour of reinforcing steel: I. The early stage of passive film formation in Ca(OH)2 solutions

Oxide film thickening on reinforcement steel at early stage of formation is followed in naturally aerated Ca(OH)₂ solutions, recalling the natural behaviour in concrete, by measuring the open-circuit potential, E, with time up to 4 h. The final potentials, E_fin, are reached from negative values indicating oxide film growth. E varies with the Ca(OH)₂ concentration according to a straight line relationship. Oxide film thickening, at early stage of immersion, follows a direct logarithmic growth law as evident from the linear relationship between E and log t. The rate of oxide film thickening deceases by increasing the concentration and pH of the solution and by raising the temperature. The free activation energy of oxide film thickening is determined and found to be 29.28 kJ/mole, indicating that the process of oxide film growth is under diffusion control.     

ESCA studies of the composition profile of low temperature oxide formed on chromium steels—II. Corrosion in oxygenated water

ESCA (Electron Spectroscopy for Chemical Analysis) has been used to analyse the chemical composition of passive films formed on chromium steels with 4–30% Cr at 25 and 70°C in oxygenated water for different times. The composition-depth profile of the films has been investigated by successive stripping of the film by ion etching.The composition of the film varies with exposure time: short time yields an Fe---Cr ratio corresponding to that of the alloy; prolonged exposure produces increasing enrichment of chromium through the whole layer, with the highest concentration at the outer surface. The passive film generally seems to consist of two layers: outermost one of (Cr(OH)₃) and underneath one of iron-chromium oxide (Fe_1+xCr_2−xO₄. The low alloy steels (3·9 and 7·8%Cr) were passive for a limited time during which the Cr enrichment was high (8 times); after breakdown of the chromium-rich passive layer, it was replaced by FeOOH.When a dry-formed oxide film, which consists mainly of iron oxide, is exposed to water, its composition slowly changes until that of a water-formed film is reached.     

Thermodynamic model for estimating the composition of passive films and Flade potential on Fe-Cr alloys in aqueous solutions

A thermodynamic model of a passive film is developed, in which the formation of the film on the surface of an Fe-Cr alloy in an aqueous solution is considered to be a result of the stable solid-phase chemical and adsorption equilibrium at the alloy-inner passive film layer interface. In the calculations, the Cr₂O₃ content in the passive film is determined by both the Gibbs energy change (ΔG < 0) in the chemical oxidation of the alloy components by the water oxygen and the change in the surface Gibbs energy (ΔG _S > 0) of the alloy. The ΔG _S change results in the negative adsorption of chromium atoms, which shifts the 3Fe + Cr₂O₃ ↔ 3FeO + 2Cr equilibrium toward the FeO formation in the passive film. Calculations showed that the enrichment of the passive film in chromium oxide should sharply increase in a chromium content range of 10–20% in the alloy, which agrees with the known data of X-ray photoelectron spectroscopy of the passive films. A formula is derived for estimating the Flade potential of Fe-Cr alloys, which relates the Flade potentials of individual Fe and Cr components to the FeO and Cr₂O₃ contents in the passive film.     

Cover Picture: Materials and Corrosion. 10/2019

Cover: The low donor density (V_o..) of the passive fi lm determines the slow electron charge transfer rate, resulting in the slow oxygen reduction rate at the film/solution interface of Ti60, which plays an essential role in ignorable galvanic corrosion of Ti60‐H62 coupling. More detailed information can be found in: Pingping Zhao, Yingwei Song, Kaihui Dong, Dayong Shan, En‐Hou Han, Effect of passive fi lm on the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62, Materials and Corrosion 2019 , 70, 1745.     

ELID grinding and tribological characteristics of TiAlN film

This paper presents the results of electrolytic in-process dressing (ELID) grinding experiments performed on TiAlN film and characterization of the tribological characteristics of the produced films. In advanced films coated by physical vapor deposition, such as CrN and TiAlN, the low surface roughness required for attaining superior tribological characteristics is difficult to attain by use of only a coating process. ELID of grinding wheels improves wheel performance, enabling the attainment of specular finishes on brittle materials, with surface roughness on the nanometer scale (4 to 6 nm). In the present study, high-quality TiAlN film surfaces were fabricated by the ELID technique, typically achieving a surface roughness of around Ra 0.0024 μm by employment of a SD#30,000 wheel. Scanning electron microscopy reveals that ELID improved the finish, as indicated by the shape of grinding marks. Chemical element analysis by an energy-dispersed x-ray diffraction system suggests that ELID grinding formed an oxide layer in the machined surface of TiAlN film. Therefore, in addition to the highly smooth surface, an oxide layer formed by ELID grinding imparts superior tribological properties to ELID-ground TiAlN film.     

Photoelectrochemical analysis of the effects of pH and sulfate ions on the structure and the composition of the passive film formed on Fe-20Cr-15Ni alloy

The effects of pH and sulfate ions on the structure and compositions of the passive film formed on Fe-20Cr- 15Ni were examined using a photoelectrochemical technique and Mott-Schottky analysis. The photocurrent spectra for the passive film formed on Fe-20Cr-15Ni in the buffer solutions are composed of two spectral components, one of which is generated from Cr-substituted γ-Fe₂O₃ and the other of which is generated from NiO. However, the passive film formed in sulfate solutions showed only the photocurrent spectrum of Cr-substituted γ-Fe₂O₃, suggesting that the formation of NiO in the passive film is suppressed because of a severe selective dissolution of Ni in the presence of sulfate ions. Mott-Schottky plots confirmed that the base structure of the passive film on Fe-20Cr-15Ni is n-type (Cr, Ni)-substituted γ-Fe₂O₃ regardless of solution pH and sulfate ions. The photocurrent intensity, flat band potential, and donor density for the passive film varied depending on the solution pH or the presence of sulfate ions in the solution, due primarily to the Cr enrichment in the film caused by the preferential dissolution of Fe and Ni that is more appreciable in highly acidic solutions containing sulfate ions.     

Effect of interfacial segregation on phase decomposition of a thin film on a patterned substrate

Numerical simulations of phase decomposition in thin films on patterned substrates are presented for a binary alloy in order to study the influence of substrate composition on microstructural evolution. For systems with a substrate composition less than the film composition, a preferential segregation ofA to the interface was observed and no phase decomposition occurred within the film. For patterned systems with a substrate composition exceeding the film composition, theB-rich phase was able to grow by a barrierless transformation for a range of film compositions outside the chemical spinodal. The number of precipitates which formed on the mesa, the dihedral angles at the three-phase trijunctions, and the resulting microstructure within the film were shown to be sensitive to the substrate composition. This article is based on a presentation made in the 2002 Korea-US symposium on the “Phase Transformations of Nano-Materials,” organized as a special program of the 2002 Annual Meeting of the Korean Institute of Metals and Materials, held at Yonsel University, Seoul, Korea on October 25–26, 2002.     

脉冲频率对HiPIMS制备TiN薄膜组织和力学性能的影响EI北大核心CSCD

为探究脉冲频率对通过高功率脉冲磁控溅射制备TiN薄膜组织力学性能的影响,选用Ti靶和N2气体,采用反应磁控溅射技术通过改变高功率脉冲磁控溅射(HiPIMS)电源脉冲频率在Si(100)晶片上制备不同种TiN薄膜。利用X射线衍射仪(XRD)、X射线光电子能谱仪和扫描电子显微镜(SEM)对所制薄膜晶体结构和成分、表面和断面形貌进行分析,利用纳米压痕仪对薄膜的硬度和弹性模量进行表征,并计算H/E和H^(3)/E^(2)。结果表明,高离化率Ti离子轰击促使薄膜以低应变能的晶面优先生长,所制TiN薄膜具有(111)晶面择优取向。薄膜平均晶粒尺寸均在10.3 nm以下,随着脉冲频率增大晶粒尺寸增大,结晶度和沉积速率降低,柱状生长明显,致密度下降,影响薄膜力学性能。在9 kHz时,TiN薄膜的晶粒尺寸可达8.9 nm,薄膜组织致密具有最高硬度为30 GPa,弹性模量374 GPa,弹性恢复为62.9%,具有最优的力学性能。     

The oxidation of cobalt in air from room temperature to 467°C

The oxidation of cobalt in air is investigated for times ranging over three orders of magnitude up to 1000 hr and for temperatures ranging from room temperature up to 467°C. Three different growth processes are observed. When a clean surface is exposed to air at room temperature, an 8–10 Åfilm of Co(OH) ₂ forms in seconds or less. For temperatures of 50–100°C, very little additional film forms for times up to 1000 hr. For temperatures of 100–225°C, a film of CoO grows in a manner which can be described empirically with a fourth root rate law with an activated rate constant. Between 225 and 325°C there is a transition to a quadratic rate law. At 425°C the film appears to be a mixture of CoO and Co ₃O₄.     

Ultrathin protective films of two-dimensional polymers on passivated iron against corrosion in 0.1 M NaCl

Prevention of iron corrosion in an aerated 0.1 M NaCl solution was investigated by polarization and mass-loss measurements of a passivated iron electrode covered with ultrathin and ordered films of two-dimensional polymers. The films were prepared on the passivated electrode by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and alkyltriethoxysilane C_nH_{2n + 1}Si(OC₂H₅)₃ (n = 8 or 18). Because crevice corrosion occurred at the initial stage of immersion in the solution preferentially, the edge of electrode covered with the polymer film was coated with epoxy resin. The open-circuit potentials of the covered electrodes in the solution were maintained high, more than −0.2 V/SCE for several hours, indicating that no breakdown of the passive film occurred on the surface. The protective efficiencies of the films were extremely high, more than 99.9% unless the passive film was broken down. The efficiencies after immersion for 24 h almost agreed with those obtained by mass-loss measurements. X-ray photoelectron spectroscopy and electron-probe microanalysis of the passivated surface covered with the polymer film after immersion in the solution for 4 h revealed that pit initiation on the passive film was suppressed by coverage with the polymer film completely.     

调制比对Cr/CrN/Cr/CrAlN多层膜结构及性能的影响

目的 探究Cr/CrN/Cr/CrAlN多层膜的最佳调制比.方法 利用电弧离子镀技术,在TC4钛合金上制备了不同调制比的Cr/CrN/Cr/CrAlN多层膜.利用扫描电子显微镜观察膜层表面和截面形貌;用Image-Pro分析软件对表面的大颗粒进行定量分析;利用X射线衍射法表征膜层的晶体结构;采用维氏硬度计测量膜层的显微硬度;采用划痕试验仪测量膜层与基体之间的结合力(临界载荷);通过基片弯曲法测量并计算得到膜层的残余应力;利用根据ASTM G76-05标准特制的AS600-喷砂试验机进行了抗冲蚀性能测试;采用三维表面轮廓仪测量冲蚀坑深度.结果 膜层表面质量和生长取向与LCr/CrN:LCr/CrAlN调制比密切相关,随着Cr/CrN比例的增加,膜层表面质量越来越好,择优取向由(111)晶面转为(200)晶面.多层膜的硬度随Cr/CrN比例的增加,呈下降趋势,结合力、残余应力和韧性则随之呈先升后降的趋势,并在LCr/CrN:LCr/CrAlN为1:2时,达到最佳.多层膜的抗砂粒冲蚀性能变化与力学性能变化一致,在LCr/CrN:LCr/CrAlN为1:2时达到最佳,其抗冲蚀能力是TC4基材的3倍以上,多层膜呈典型的脆性断裂失效形式.结论 在调制比LCr/CrN:LCr/CrAlN=1:2时,膜层获得最佳的抗冲蚀性能.     

Whole pH range anti-corrosion property of aluminium alloy coated with MFI zeolite film

ABSTRACT

Strong protection capability of zeolite coating for AA6061 substrate from corrosion in NaCl, H₂SO₄ and NaOH solution has been demonstrated with reduction of corrosion current by five orders of magnitude. Film resistance was identified as the governing parameter in the formation of a barrier shielding the penetration of aggressive species. For the MFI zeolite film growth on the surface of the AA6061 substrate, while the in situ crystallisation (InC) protocol generated loosely packed film made of large zeolite crystal, the dry-gel conversion (DGC) protocol prepared dense film comprising of nanoparticles. Superior protection ability of DGC-grown film is attributed to the increased film resistance associated with a dense and impermeable zeolite layer. As such, the DGC-grown film requiring thinner film thickness around 5?μm showed better anti-corrosion function than the InC-grown film.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Study of electronic‐ionic conducting transformation of temporarily protective oil coating in salt solution

In this paper, a multiple microelectrode array was developed to study the electronic‐ionic conducting transition of temporarily protective oil coating in salt solution. It was pointed out that there existed electronic‐ionic transition of temporarily protective oil coating in salt solution varying with immersion time. At the early stage of immersion, the oil coating was an electronic conductor, which having very low conductivity. With increasing of immersion time, the oil coating transformed from electronic conductor to ionic conductor, where ionic diffusion in the coating was predominant. Based upon Bailey and Ritchie's general electrochemical theory for the oxidation of metals, an electrochemical analysis of potential inhomogeneity of the oil coating was presented. It was assumed that only one step could be rate‐determining in the overall reaction in the metal/oil film/solution system. It was predicted that there were two kinds of film in the temporarily protective oil coating, ionic and electronic conducting film. For the ionic conducting film, potentials of oil coated electrode were equal to equilibrium potential of metal oxidation at the metal/coating interface (E_a^eq), and it had the most negative value. For the electronic conducting film, potentials obtained were equal to the equilibrium potential of the oxidant reduction at the coating/electrolyte interface (E_c^eq), and it had the most positive value. Potential measurements in this paper verified the results of Wormwell and Brasher's research in 1949; the distribution of potential on oil‐painted wire beam electrodes being heterogeneous and following a discontinuous binomial probability distribution were also elucidated.     

Effect of Cu additive on the structure and magnetic properties of （CoPt）1-xCux films

CoPt thin films with various Cu contents varying from 0 vol.% to 21.5 vol.% were deposited on glass substrates by magnetron sputtering. The effects of Cu additive on the structural and magnetic properties and the ordering temperature of CoPt films were investigated in detail. The results show that the Cu in CoPt films plays an important role in promoting the ordering parameter S and reducing the ordering temperature of CoPt films. A nearly perfect (001) texture was obtained in a CoPt film doped with 15.3 vol.% Cu. Besides, the preferred orientation of the CoPt film can be changed by annealing temperature. The perpendicular growth of the CoPt film is favored at a high annealing temperature.     

Corrosion protection of molybdate doped polypyrrole film prepared in succinic acid solution

ABSTRACT

Polypyrrole (PPy) was prepared on the mild steel substrate by electrochemical polymerisation in the solution containing pyrrole monomer and succinic acid. The mild steel surface could be passivated before and during electropolymerisation by molybdate. The morphology and structure of the PPy film were studied with SEM. The typical cauliflower structure of PPy was observed. Raman and IR spectroscopy showed that the obtained PPy was in an oxidised state. The thermal stability of PPy was investigated by the thermal gravimetric analysis, showing that PPy was stable at higher than 480°C. The electrochemical property of the PPy film was performed by open circuit potential, polarisation curves (I/E), and electrochemical impedance spectroscopy. The corrosion behaviour of mild steel (CT3) with PPy film in solution NaCl 3% was studied.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Effect of porous silicon layer on the performance of Si/oxide photovoltaic and photoelectrochemical cells

Photovoltaic and photoelectrochemical systems were prepared by the formation of a thin porous film on silicon. The porous silicon layer was formed on the top of a clean oxide free silicon wafer surface by anodic etching in HF/H₂O/C₂H₅OH mixture (2:1:1). The silicon was then covered by an oxide film (tin oxide, ITO or titanium oxide). The oxide films were prepared by the spray/pyrolysis technique which enables doping of the oxide film by different atoms like In, Ru or Sb during the spray process. Doping of SnO₂ or TiO₂ films with Ru atoms improves the surface characteristics of the oxide film which improves the solar conversion efficiency.The prepared solar cells are stable against environmental attack due to the presence of the stable oxide film. It gives relatively high short circuit currents (I_sc), due to the presence of the porous silicon layer, which leads to the recorded high conversion efficiency. Although the open-circuit potential (V_oc) and fill factor (FF) were not affected by the thickness of the porous silicon film, the short circuit current was found to be sensitive to this thickness. An optimum thickness of the porous film and also the oxide layer is required to optimize the solar cell efficiency. The results represent a promising system for the application of porous silicon layers in solar energy converters. The use of porous silicon instead of silicon single crystals in solar cell fabrication and the optimization of the solar conversion efficiency will lead to the reduction of the cost as an important factor and also the increase of the solar cell efficiency making use of the large area of the porous structures.     

Low field magnetoresistance properties of (La0.75Sr0.25)1.05Mn0.95O3 polycrystalline thin films on a-SiO2/Si substrates prepared by ex-situ solid phase crystallization

We report the low field magnetoresistance (LFMR) properties of (La_0.75Sr_0.25)_1.05Mn_0.95O₃(LSMO) films on a-SiO₂/Si substrates, prepared by ex-situ solid phase crystallization of amorphous films deposited by dc-magnetron sputtering at room temperature. The average grain size of the LSMO films was gradually increased with increasing annealing temperature (T _an ) and film thickness. High T _an also caused the growth of an amorphous inter-diffusion layer between a-SiO₂ and LSMO. The highest LFMR values of 16 and 1.0 % were achieved at 100 K, 1.2 kOe and 300 K, 0.5 kOe, respectively, from an LSMO film of 200 nm thickness annealed at 900 °C. In accordance with a modified brick layer model, grain boundary areal resistance gradually increased with increasing T _an and decreasing film thickness due to the penetration of the amorphous inter-diffused phase into the LSMO grain boundary. Improved LFMR values are attributable to modification of the LSMO grain boundary into a more effective spin-dependent scattering center.     

Pre-annealing effect of electroless Ni−B deposit as a diffusion barrier for electroplated Cu electrodes

Ni−B film of 1 μm thickness was electrolessly deposited on an electroplated Cu bus electrode. The film, which encapsulates the Cu bus electrodes, prevents Cu oxidation and serves as a diffusion barrier against Cu contamination of the transparent dielectric layer in a plasma display during the firing process at 580 °C. The microstructure of theas-deposited barrier film was amorphous phase and crystallized to Ni and Ni₃B after annealing at 300 °C. The good barrier properties observed here can be explained by Ni₃B precipitates at the grain boundaries acting as a fast diffusion path via pre-annealing at 300 °C before the firing process at 580 °C.     

Protection of passivated iron from corrosion in 0.1 M KClO4 with and without Cl by coverage with a two-dimensional polymer film of carboxylate ion self-assembled monolayer

A film of two-dimensional polymer was prepared on an iron electrode passivated in a borate buffer solution at pH 8.49, derivatized with 16-hydroxyhexadecanoate ion and then modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. The protective ability of the polymer film adsorbed on passivated iron was examined by polarization measurement in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ and 1 × 10⁻³ M of Cl⁻. The values of the open-circuit potential, E_oc were monitored with the immersion time, t in these solutions. The E_oc value of the passivated electrode in 0.1 M KClO₄ was maintained high, more than −0.2 V/SCE in the initial region of t up to 10 h, indicating the presence of a passive film on the electrode. Thereafter, E_oc decreased to −0.4 V/SCE abruptly, exhibiting breakdown of the passive film. The value of the passivated electrode covered with the polymer film remained almost constant around −0.04 V/SCE during immersion for 45 h. The protective efficiency, P (%) of the polymer film on passivated iron was extremely high, more than 99.9% unless the passive film was broken down, indicating complete protection of iron against corrosion. The times for breakdown on the passivated electrode and polymer-coated one diminished with an increase in the concentration of Cl⁻. The polymer-coated surface was analyzed by electron-probe microanalysis after immersion in 0.1 M KClO₄ for 24 h.