Detection of sigma phase in 22% Cr duplex stainless steel by electrochemical methods

Duplex stainless steels (DSS) may undergo various structural transformations as a function of temperature, leading to formation of secondary phases when exposed to temperatures in the range 600–1000°C for prolonged periods of time. Among these phases, apart from carbides and nitrides, sigma is the most prominent intermetallic compound, since it is known to adversely affect mechanical properties and corrosion resistance of DSS as a consequence of Cr and Mo depletion in the boundary zones of ferrite grains. As a result of sigma precipitation, DSS become susceptible to localized corrosion via a mechanism resembling sensitization in austenitic stainless steels. Electrochemical methods, known to successfully detect sensitization in austenitic SS, have been used to identify reliable test conditions with appropriate sensitivity also for DSS. A modified electrochemical potentiokinetic reactivation method was developed to investigate 22% Cr DSS sensitivity under different thermal cycles. Modifications were designed by closely analysing DSS anodic behaviour changes with respect to the operating testing conditions. All findings were confirmed by SEM, optical microscopy and XRD.     

Electrochemical behavior of Ni-Al-Fe alloys in simulated human body solution

An investigation about the corrosion resistance of Ni-Al-Fe intermetallic alloys in simulated human body fluid environments has been carried out using electrochemical techniques. Tested alloys included 57 (wt%) Ni-(20 to 30) Al-(12 to 23) Fe using the Hank's solution because the high corrosion resistance provided by protective Al₂O₃ external layer. For comparison, AISI 316L type stainless steel has also been used. Electrochemical techniques included potentiodynamic polarization curves, electrochemical impedance spectroscopy, and electrochemical noise measurements. The different techniques have shown that these alloys showed a similar or higher corrosion resistance than conventional AISI 316L type stainless steel, and this corrosion resistance decreased as the Al content in the alloy increased. The alloys were susceptible to pitting type of corrosion on the interdendritic Ni-rich phases.     

Formation of Al‐enriched surface layers through reaction at the Mg‐substrate/Al‐powder interface

Al‐enriched surface layers containing a Mg₁₇Al₁₂ intermetallic phase and a solid solution of Al in Mg were fabricated by heating Mg specimens in contact with Al powder in a vacuum furnace. The layer formation process proceeded through partial melting at the Mg‐substrate/Al‐powder interface. The test results suggest that a good contact between the Al powder and the Mg substrate is required during heat treatment. In this study, a pressure of 1 MPa was applied to improve the contact of the Al powder with the Mg specimen. When the powder was pressed down during heating, it was possible to reduce the process temperature from 450 °C to 440 °C. The layers produced at 440 °C in a short heating time (40 min) were thick, continuous and uniform. The microhardness of the Al‐enriched layers was much higher than that of the Mg substrate. The results of the electrochemical corrosion tests indicated that the Mg specimens with an Al‐enriched surface layer had better corrosion resistance than the bare Mg. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of the Acid Passivation of Stainless Steel

Abstract

Passivation of 304 and 316 stainless steels in various acid solutions was studied as a function of exposure time and acid concentration. Nitric acid, citric acid, and the commercial Citrisurf (a commercial citric acid–based passivating solution, Stellar Solutions, USA) were compared. The materials were studied by low‐angle PXRD (powder x‐ray diffraction), XRF (x‐ray fluorescence), SEM (secondary electron microscopy), and XPS (x‐ray photoelectron spectroscopy). As might be expected, the measurements showed increased Cr:Fe ratios at the surface following acid passivation. Using the combination of characterization methods, it was possible to generate concentration‐depth profiles, and these suggest that chromium enrichment can penetrate several micrometers into the surface for nitric acid treatment, and this is related to some surface damage. The low‐angle PXRD work illustrated that complex phases are formed at the passivated surface, and these phases exhibit a rich structural chemistry. It is concluded that citric acid–based passivating agents result in more coherent oxide surfaces that are more resistant to corrosion.     

Electrochemical response of natural and induced passivation of high strength duplex stainless steels in alkaline media

The passivation of two high strength duplex stainless steels (HSSS) was investigated in alkaline solutions simulating the pore solution of concrete by the growth of natural and induced passive films. Induced passive films were generated both by cyclic voltammetry and by chronoamperometry. Natural passive films were spontaneously grown by the immersion of the steel in the alkaline electrolyte. These passive layers were characterised by electrochemical impedance spectroscopy, corrosion current density (i _corr) and corrosion potential (E _corr) monitoring. The effect of significant parameters, such as the pH in the HSSS/alkaline solution interface, the composition of the duplex stainless steels and the ageing of the passive layer, on the electrochemical performance of both induced and spontaneously grown passive films has been analysed. The increase of alkalinity highly influences the electrochemical performance of the passive film by promoting the formation of a passive layer with a less resistant electrochemical response. The electrochemical behaviour of the passive layer is also affected by the alloying elements like Mo or Ni. Both natural and induced passive films show similar electrochemical trend with respect to significant parameters such as the pH and the composition of the steel. The ageing of the spontaneously grown passive layer promotes a higher resistive electrochemical response which might be related to the enrichment of the passive layer in non-conducting (or semi-conducting) oxides.     

Protective coatings based on Mn-Co spinel for current collectors of solid oxide fuel cells

The method of electrostatic spray pyrolysis was designed to apply protective coatings based on Mn-Co spinel to ferrite stainless steels (Crofer22APU and 08Kh18T1). The comparative thermogravimetric (TG) studies of ferrite stainless steels with and without protective coatings were carried out. The electrochemical characteristics of protective coatings exposed to long current loading were studied. The formation processes of Cr₂O₃ oxide films were studied at the contact of ferrite stainless steel with La_0.8Sr_0.2MnO₃ ionic and electronic conductor. The coatings of Mn-Co spinel were shown not preventing formation of continuous oxide film on the stainless steel surface.     

双相不锈钢的选择性腐蚀研究(英文)

双相不锈钢中的铁素体(α相)和奥氏体(γ相)具有不同的晶体结构和化学成分,使之在水溶液环境中表现不同的耐蚀特征.本文应用空间分辨电化学技术测量2205双相不锈钢中铁素体和奥氏体的电位差异,并用电镜技术分析了α相和γ相的选择性腐蚀形态.结果表明,在0.01mol/LNaCl溶液中,铁素体的腐蚀电位比奥氏体高,而在2mol/LH2SO4+xmol/LHCl溶液中,双相不锈钢在活化＿钝化电位区出现两个明显的阳极电流峰.铁素体相的选择性腐蚀发生在较负的阳极峰电位,而奥氏体则在较正的阳极电位峰发生选择性腐蚀.     

The effect of molybdenum on corrosion of low-temperature nitrided stainless steels in sulphate–chloride solution

Resistance of stainless steels to pitting corrosion is strongly enhanced by nitriding at 380–450°C. In this work, anodic behaviour of steels with 0.13, 2.1, 4.5 and 6.1 wt% Mo was studied before and after nitriding at 450°C for 30 h which gave 13.0–15.8 wt% N at the surface. Electrochemical measurements were carried out in 0.1 M Na₂SO₄ + 0.4 M NaCl at pH 3.0. Nitriding of steels with lower Mo contents (0.13 and 2.1 wt% Mo) enhanced the resistance to pitting corrosion; steels with higher Mo contents retained their high resistance to pitting but underwent an activation. Nitrogen increased anodic reactivity in initial stages of polarisation, and it also increased the passivation rate. X-ray photoelectron spectroscopy analysis showed that anodic films on nitrided steels contained oxides at the outer surface and Cr–N species deeper from the surface. The enhanced resistance to pitting corrosion of low-temperature nitrided steels is explained by the increased anodic reactivity which leads to the formation of a salt-type film with Cr/Fe oxides and Cr–N species.In Honour of Professor Kurt Schwabe.     

In Situ Study of the Surface Oxidation of FeCr Alloys Using Grazing Incidence X‐ray Absorption Spectroscopy (GIXAS)

The surface oxidation of FeCr alloys with 18, 28, and 43 mass‐% Cr was investigated in situ using grazing‐incidence X‐ray absorption spectroscopy (GIXAS) at the chromium and iron K‐edges. Oxidation in air was monitored in situ in the temperature range from 290 K to 680 K. The standard GIXAS data analysis is extended for the treatment of a single layer model in order to estimate the chromium concentrations of the oxide layer and of the near‐interface substrate as well as the oxide layer thickness. XANES analysis shows transitions from b.c.c. Fe to corundum type Fe₂O₃ and from b.c.c. Cr to corundum type Cr₂O₃. The initial oxide layers are 1.1‐1.4 nm thick and contain 60‐90 mass‐% chromium, while the near‐interface substrate is depleted in Cr. During heating, iron oxide growth dominates up to 560‐600 K. Then the chromium oxide layer loses its passivation effect and Cr oxidation sets in.     

Comments on: “Toward improved heat transfer performance of annular heat exchangers with water/ethylene glycol based nanofluids containing graphene nanoplatelets,Journal of Thermal Analysis and Calorimetry 126.3 (2016): 1427–1436”

The present study has investigated the complex mechanisms in the aluminum–titanium system with different percentages of titanium through a combination of thermal and X-ray analyses. Thermogravimetry, derivative thermogravimetric, X-ray diffraction, scanning electron microscope and transition electron microscope were used for characterization of the samples. Initially, different Al–Ti powder mixtures were produced by high-energy ball milling and after 30 h of milling the phases generated at different percentages of Ti were analyzed. The XRD results revealed that the intermetallic Al₃Ti powder is obtained after a certain duration of milling. In addition, L1₂ to D0₂₃ phase transformation is possible with increase of the Ti percent. Analyses of the powder annealed at different temperatures yielded interesting results, including the effect of stearic acid as the surface control agent on phase transformations of the aluminum–titanium system and also the formation of unexpected phases such as Al₄C₃ and TiC. Moreover, ductile to brittle transition during phase transformations of the intermetallic Al₃Ti powder was quite conspicuous, which could result in more homogeneity of the powders and the occurrence of more reactions in the system. For example, formation of D0₂₃-Al₃Ti powder which is more brittle compared to L1₂ resulted in the exit of Al from among its layers, leading to the increase of the chances for Al reaction with the system impurities.     

A Quartz Crystal Microbalance Characterization of Metal‐Oil Interfaces and Interactions with Wax Molecules

The solid‐liquid interface between stainless steel and model petroleum fluids is investigated at isothermal conditions using a quartz crystal microbalance. AISI 316 (Fe/Cr18/Ni10/Mo3) stainless steel is chosen to represent the metal surface. Paraffin components dissolved in dodecane constitute the petroleum fluid phase. Commercial macro‐crystalline and micro‐crystalline waxes provide primarily linear and branched paraffin components, respectively. Paraffin solubility conditions are established through a van't Hoff relationship. Model fluids prepared with the single‐component alkanes n‐C₃₆ or n‐C₃₀ paraffin provide well‐defined solubility conditions. Monitored changes in resonance frequency and energy dissipation of the quartz crystal resonator immersed in the model fluids confirm that no continual deposition of paraffin components occurs at isothermal conditions. Solid paraffin crystals dispersed in solution show no adherence to the stainless steel surface. The absence of attractive interactions between the stainless steel surface and the dispersed paraffin crystals suggests that a surface adsorption and/or surface nucleation mechanism is responsible for the formation of incipient paraffin wax deposits under nonquiescent conditions.     

Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species

The structure of FeO_x species supported on γ‐Al₂O₃ was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al₂O₃ and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe₂O₃ particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al₂O₃ surface.     

Surface Modification by Compositionally Modulated Multilayered Zn‐Fe Alloy Coatings

Compositionally modulated multilayered alloy (CMMA) coatings of Zn-Fe were developed from acid chloride baths by single bath technique. The production and properties of CMMA Zn-Fe coatings were tailored as a function of switching cathode current densities (SCCD’s) and thickness of individual layers. Corrosion rates (CR) were measured by electrochemical methods. Corrosion resistances were found to vary with SCCD’s and the number of sub layers in the deposit. SCCD’s were optimized for production of Zn-Fe CMMA electroplates showing peak performance against corrosion. The formation of discrete Zn-Fe alloy layers having different compositions in the deposits were demonstrated by scanning electron microscopy (SEM). Improvements in the corrosion resistance of multilayered alloys are due to the inherent barrier properties of CMMA coatings as evidenced by electrochemical impedance spectroscopy (EIS). Corrosion resistance afforded by Zn-Fe CMMA coatings are explained in terms of the n-type semiconductor films at the interface, supported by Mott-Schottky’s plot. It was observed that the alloy with high w(Fe) on the top showed better corrosion resistance compared to that with the less w(Fe) on top. At optimum SCCD’s of 3.0—5.5 A•dm－2, a Zn-Fe CMMA coatings with 600 sub layers showed ca. 45 times better corrosion resistance than conventional Zn-Fe alloy of the same thickness. The deposit showed no red rust even up to 1130 h in salt spray test.     

铝合金表面电偶腐蚀与电子功函数的关系

铝合金中经常会引入一些第二相来改善其性能,第二相由于和铝基体的电位差不同,将会对铝合金的局部腐蚀产生重大的影响.为了揭示铝合金腐蚀的物理本质,本文利用基于密度泛函理论第一性原理的计算方法,详细计算了铝合金中一些主要第二相(Al_2Cu、Al_3Ti和Al_7Cu_2Fe)的多种晶面的电子功函数,分析了电子从各个晶面逸出的难易,求得了第二相与Al基体的本征电势差,我们发现不同的晶面暴露在合金最外层,会显著地影响本征电势差;即便是同一晶面,暴露在最外层的原子种类和构型不同,对腐蚀的影响也不一样.从电子的层面解释了电偶腐蚀发生的原因.     

Study on the cluster of floating dross before nucleating during hot-dipping process

At present, hot-dipping anticorrosion metalliccoating on the surface of steel base is the main methodto prevent atmospheric corrosion of steel. With thechange of atmospheric environment, the traditionalidea of hot-dipping pure Zn cladding already does not…     

Computational insights into the molecular mechanisms for chromium passivation of stainless-steel surfaces

First principles DFT calculations are used to gain insights into the molecular mechanism of Cr passivation of FeCr alloy surfaces. The systems studied represent early stages of oxidation of FeCr alloys when the oxide layers extend just a few atomic layers into the bulk. A Monte-Carlo atom-swapping algorithm was developed to efficiently explore possible atomic positions and identify the most promising structures that yield overall energy lowering. Analysis of the resulting low energy structures show that the surface oxide layer is rich in chromium while there is a reduction in chromium in the metallic phase near the alloy-oxide interface. Furthermore, there is an increased concentration of Fe near the oxide-air surface. Analysis of the molecular structure of the oxide layers found that oxidized Cr was predominantly in the Cr₂O₃ phase, while oxidized Fe was present as both FeO and Fe₂O₃. We propose that the oxidative variability of Fe facilitates O diffusion in the iron-rich phases because of the range of geometries available for accommodating the O atom. In contrast, O diffusion is less facile in Cr, which has little variability in oxidation state.     

Thermodynamic study of the zirconium-aluminum system

The heats of formation of the zirconium-aluminum intermetallic compounds ZrAl₃, ZrAl₂, Zr₂Al₃, ZrAl, Zr₅Al₄, Zr₃Al₂, Zr₅Al₃, and the solid solution of aluminum in bcc zirconium have been studied using a Knudsen cell mass spectrometric technique. The high-temperature compound Zr₅Al₄ was identified in the residue of some of these experiments and this led to further heat treatment/X-ray diffraction experiments which indicated that Zr₄Al₃, previously reported to form from the melt, decomposes in the solid state at temperature in excess of 1050°C. By measuring aluminum vapor pressures over the two-phase ranges of the system from 0 < X_Al < 0.75 the enthalpy changes for the decomposition reactions were determined by second- and third-law methods, and these were used along with the measured vapor pressure of aluminum over the solid solution of aluminum in bcc zirconium to derive the enthalpies of formation of the intermetallic phases (in kcal/mole): ZrAl₃, ?38.96; ZrAl₂, ?32.86; Zr₂Al₃, ?56.12; ZrAl, ?21.36; Zr₅Al₄, ?93.76; Zr₃Al₂, ?48.78; Zr₅Al₃, ?74.57.     

Production of 5‐Hydroxymethylfurfural from Fructose in Ionic Liquid Efficiently Catalyzed by Cr(III)‐Al2O3 Catalyst

A series of metal‐Al₂O₃ catalysts were prepared simply by the conventional impregnation with Al₂O₃ and metal chlorides, which were applied to the dehydration of fructose to 5‐hydroxymethylfurfural (HMF). An agreeable HMF yield of 93.1% was achieved from fructose at mild conditions (100°C and 40 min) when employing Cr(III)‐Al₂O₃ as catalyst in 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl). The Cr(III)‐Al₂O₃ catalyst was characterized via XRD, DRS and Raman spectra and the results clarified the interaction between the Cr(III) and the alumina support. Meanwhile, the reaction solvents ([Bmim]Cl) collected after 1^st reaction run and 5^th reaction run were analyzed by ICP‐OES and LC‐ITMS and the results confirmed that no Cr(III) ion was dropped off from the alumina support during the fructose dehydration. Notably, Cr(III)‐Al₂O₃ catalyst had an excellent catalytic performance for glucose and sucrose and the HMF yields were reached to 73.7% and 84.1% at 120°C for 60 min, respectively. Furthermore, the system of Cr(III)‐Al₂O₃ and [Bmim]Cl exhibited a constant stability and activity at 100°C for 40 min and a favorable HMF yield was maintained after ten recycles.     

Thermodynamic analysis of (Ni,Fe)3Al formation by mechanical alloying

(Ni, Fe)₃Al intermetallic compound was synthesized by mechanical alloying (MA) of Ni, Fe and Al elemental powder mixtures of composition Ni₅₀Fe₂₅Al₂₅. Phase transformation and microstructure characteristics of the alloy powders were investigated by X-ray diffraction (XRD). The results show that mechanical alloying resulted in a Ni (Al, Fe) solid solution. By continued milling, this structure transformed to the disordered (Ni, Fe)₃Al intermetallic compound. A thermodynamic model developed on the basis of extended theory of Miedema is used to calculate the Gibbs free-energy changes. Final product of MA is a phase having minimal Gibbs free energy compared with other competing phases in Ni–Fe–Al system. However in Ni–Fe–Al system, the most stable phase at all compositions is intermetallic compound (not amorphous phase or solid solution). The results of MA were compared with thermodynamic analysis and revealed the leading role of thermodynamic on the formation of MA product prediction.     

Determination of Nitrogen in Duplex Stainless Steels by EPMA

 We describe the quantitative determination of low nitrogen contents (< 1 %wt) in highly-alloyed, duplex stainless steels by EPMA using a calibration curve. Five monophasic stainless steels with various nitrogen concentrations were used for the calibration curve, namely, three highly alloyed steels prepared in the laboratory, with nitrogen contents 0.066, 0.565 and 1.016 %wt and two industrial alloys with nitrogen concentrations 0.174 %wt and 0.023 %wt. For these samples, the plot of nitrogen X-ray intensities versus nitrogen contents exhibited an acceptable linear relationship. Average nitrogen contents of the analysed duplex alloys were found to vary in the range < 0.045–0.07 %wt in ferrite and 0.52–0.77 %wt in austenite. These results suggest that the nitrogen solubility limit in ferrite has been reached; on the other hand, nitrogen solubility in austenite increases due to the high manganese and low nickel contents.