Cr/SSZ-13催化二氧化碳氧化乙烷脱氢反应的研究

通过脱氢反应将低碳烷烃转化为同碳数的烯烃是烷烃高值化利用和烯烃原料多元化的重要途径。烷烃氧化脱氢制烯烃的反应具有不受反应平衡限制、积炭少、反应温度低等优点,一直是研究的热点。通过利用浸渍法制备不同铬（Cr）负载量的Cr_x/SSZ-13系列催化剂,采用氮气物理吸附、氨程序升温脱附（NH₃-TPD）、二氧化碳程序升温脱附（CO₂-TPD）、氢气程序升温还原（H₂-TPR）、紫外-可见吸收光谱（UV-Vis）以及高角度环形暗场-扫描透射电镜（HAADF-STEM）与耦合能谱分析（EDX-Mapping）等方法对催化剂进行了物性表征,并用微型固定床反应器评价催化剂对乙烷氧化脱氢制乙烯的催化性能,最终建立了Cr/SSZ-13催化剂的构效关系。研究发现,当n（二氧化硅）/n（氧化铝）=10时,Cr_1.5/SSZ-13-10催化剂上含有丰富的Cr³⁺物种,其中配位不饱和Cr³⁺是优异的脱氢活性位,有利于二氧化碳氧化乙烷脱氢反应的进行。因此,Cr_1.5/SSZ-13催化剂在650 ℃时表现出优异的催化性能,即二氧化碳转化率和乙烷转化率分别达到26.41%和53.2%,乙烯产率为38.83%。     

超级13Cr不锈钢腐蚀性能的研究现状与进展

针对超级13Cr不锈钢管材料在各种环境下所面临的腐蚀问题,介绍了其CO2腐蚀机理及其影响因素,分析了腐蚀产物膜成分破坏机理,简要说明了超级13Cr不锈钢几种常见的腐蚀类型,并提出了今后超级13Cr不锈钢及其腐蚀行为研究的重要方面,为今后油套管材料提供参考。     

Immobilizing chromium in stainless steel slags with MnO addition

This work investigates the stabilizing impact of MnO on the leaching behavior of hazardous Cr-containing CaO-SiO₂-Al₂O₃-Cr₂O₃-MnO stainless steel slags after equilibrating at various elevated temperatures and evaluates the potential immobilization of Cr into a MnCr₂O₄ spinel phase from the existing Cr₂O₃ phase. The MnCr₂O₄ spinel phase was found to be an excellent Cr-stabilizer in stainless steel slags, where the leaching tendency of potentially hazardous Cr-related ions decreased with higher MnO content and lower equilibration temperatures within the range of 0 to 15 mass pct. and 1500 to 1300°C, respectively. Thermodynamic calculations by conducting the phase stability diagram also showed that the MnCr₂O₄ spinel phase was relatively stable and the Ca₃Si₂O₇ (Ca_3-xMn_xSi₂O₇) phase was relatively unstable compared with other crystal phases in acid extractant with pH value of 3.2. Combined with the scanning electron microscopy and X-ray powder diffraction results along with the thermodynamic calculations, the leached Cr-related ions was predominantly originating from the unstable amorphous glass phase.     

正交实验法对20#碳钢在油田采出水中的应用研究

为了研究20#碳钢材料在油田上的适用范围,采用室内静态腐蚀挂片正交实验法,模拟油田采出水腐蚀性因素对20#碳钢在油田采出水中的应用进行了探讨。根据腐蚀失重法及试片的腐蚀速率分析,利用正交实验考察ρ(Ca2+)、ρ(HCO3-)、ρ(Cl-)、温度、pH值对20#碳钢腐蚀行为的影响。结果表明,对20#碳钢腐蚀性影响的强弱程度为温度pH值ρ(Cl-)ρ(HCO3-)ρ(Ca2+)。温度对20#碳钢起主要的影响,其腐蚀速率随温度升高而升高。同时,腐蚀速率随pH值增大而降低。其次,ρ(Cl-)的增加使低碳钢腐蚀加重,ρ(Ca2+)、ρ(HCO3-)对20#碳钢也有一定程度的腐蚀作用。     

The electrochemical behaviour of stainless steel AISI 304 in alkaline solutions with different pH in the presence of chlorides

Nowadays, stainless steel reinforcements appear as an effective solution to increase the durability of reinforced concrete structures exposed to very aggressive environments. AISI 304 is widely used for this purpose. Although the improved durability of reinforcing AISI 304, when compared to carbon steel, there is a high probability of pitting susceptibility in the presence of chlorides. Thus, the present work aims at studying the passivation and passivation breakdown of AISI 304 in alkaline solutions of different pH (pH from 13 to 9), simulating the interstitial concrete electrolyte. These solutions were contaminated with different concentrations of chloride ions (3% and 10%, as NaCl). The electrochemical behaviour was evaluated by d.c. potentiodynamic polarization and by electrochemical impedance spectroscopy (EIS).The morphological features and the changes observed in the surface composition were evaluated by Scanning Electron Microscopy (SEM) together with EDS chemical analysis.The results evidence that pH plays an important role in the evolution of the film resistance and charge transfer processes. Moreover, the effect is highly dependent upon the chloride content and immersion time.     

ICP—AES法测定不锈钢中铬的精密度研究

进行了电感耦合等离子体发射光谱法（ICP-AES）测定不锈钢中铬元素的精密度研究,运用排除法确定了导致不锈钢中测量铬元素精密度稳定性较差的主要原因是仪器自身的波动。不锈钢中铬元素的激发状态、溶液黏度、酸度以及操作过程对方法精密度的影响不明显。加入内标钪元素后,不锈钢中铬元素测量的相对标准偏差（RSD）由原来的0．60％～1．60％降低到≤0．50％,精密度明显提高。同时,不锈钢中铬元素测定的准确度也得到提高。     

Electrodeposition of poly(N-methylpyrrole) on stainless steel in the presence of sodium dodecylsulfate and its corrosion performance

Poly(N-methylpyrrole)-dodecylsulfate (PNMPy-DS) coating was electrosynthesized by potentiodynamic method on a stainless steel in oxalic acid solution containing sodium dodecylsulfate for the first time. The effects of electrochemical synthesis parameters, such as applied potential, scan rate and cycle number, on the protective behaviors of PNMPy-DS films were investigated and the optimum synthesis conditions were determined. The PNMPy-DS coating was characterized by the cyclic voltammetry, FT-IR spectroscopy and SEM methods. Corrosion protection behavior of this polymer-coated steel was investigated in 0.5 mol L⁻¹ HCl solution by potentiodynamic polarization and EIS methods. The results show that the PNMPy-DS coating provides effective protection for the stainless steel against to corrosion due to the fact that the large negatively charged dodecylsulfate dopant in the polymer structure electrostatically repels corrosive chloride ions and delays their access to metal surface.     

Influence of laser surface hardening on the corrosion resistance of martensitic stainless steel

Martensitic high nitrogen stainless steels offer a combination of wear-, corrosion- and fatigue properties. But for some applications a higher surface hardness is required. A laser hardening with rapid heating (without smelting) and cooling (quenching) rates can improve the surface hardness with compressive residual stresses in the near surface layer. Yet, some cases of pitting corrosion in chloride media are reported.In this study, the influence of process parameters, composition of the atmosphere and the overlapping ratio, has been investigated. With complementary surface analytical methods and electrochemical techniques the relation between surface structure and composition and corrosion behavior in chloride media has been studied.It has been shown that, during the laser treatment the surface must be shielded with argon in order to avoid the formation of a porous layer of iron oxides, which is dramatically detrimental to the corrosion resistance.After the laser treatment a mixture of martensite and retained austenite is obtained, depending on the surface temperature and overlapping ratio. With a surface temperature of 1200 °C and a minimal overlapping ratio (10%), a thin surface layer of retained austenite, wherein nitrides are dissolved, improves the corrosion resistance. The hardness increases with the amount of distorted martensite and reaches a maximum at 1000 °C.     

CO_2-EOR环境碳钢和Cr13钢腐蚀产物膜稳定性研究的展望

从CO2腐蚀产物膜稳定性出发,对CO2腐蚀过程中影响碳钢和Cr13钢产物膜稳定性的因素进行了综述,提出了目前存在的问题和解决的方向。     

Corrosion and passivation behaviors of some stainless steel alloys in molten alkali carbonates

The corrosion and passivation behaviors of two types of stainless steel alloys (ferritic and austenitic steels) in ternary molten Li₂CO₃-Na₂CO₃-K₂CO₃ mixture at different temperatures (475-550 °C) were studied using galvanostatic polarization and cyclic voltammetry. The galvanostatic polarization curves of the investigated alloys illustrate the passivation and passivity breakdown of the alloys. The passivation potential range for the three investigated steel alloys is about 1.15-1.3 V. During this potential range different oxide and spinels are formed, the nature of which depends on the type of alloy and the anodization potential. At high anodic potentials the decomposition of carbonate takes place, leading to passivity breakdown and oxygen evolution. The values of corrosion parameters (R_p, i_o and i_corr) were calculated. The calculated values indicate that the corrosion resistance of the austenitic stainless steel is higher than that of the ferritic steel. The activation energy of the corrosion process was found to be equal to about 70 kJ mol⁻¹. The results of the cyclic voltammetric investigations indicate that the behavior of the austenitic steels is about the same and differs from that of ferritic steel. The corrosion tests in 0.2 M HCl solutions have shown that the oxide scales formed on the surface of the austenitic stainless steels are multilayered, whereas those formed on the ferritic alloy are uniform.     

Corrosion inhibition of mild steel in acidic media by Basic yellow 13 dye

The inhibition performance of Basic yellow 13 dye on mild-steel corrosion in hydrochloric acid solution was studied at 25 °C using weight loss and electrochemical techniques. The effect of inhibitor concentration on inhibition efficiency has been studied. Inhibition efficiency increased with increase of Basic yellow 13 concentration. The results showed that this inhibitor had good corrosion inhibition even at low concentrations (95% for 0.005 M Basic yellow 13) and its adsorption on mild-steel surface obeys Langmuir isotherm. ΔG _ads was calculated and its negative value indicated spontaneous adsorption of the Basic yellow 13 molecules on the mild-steel surface and strong interaction between inhibitor molecules and metal surface. The value of ΔG _ads was less than 40 kJmol⁻¹, indicating electrostatic interaction between the charged inhibitor molecules and the charged metal surface, i.e., physical adsorption.     

Effect of dissolved chromium species on the corrosionof stainless steel in nitric acid

The effect of Cr(vi) species in HNO3 (concentrations 15–3m) on the corrosion rate of stainless steel has been investigated. The gaseous phase over the HNO3 was carefully controlled using Ar, NO, NO2 or N2 purging. With Ar purging the corrosion rate increased when the Cr(vi) concentrations were above 0.05m. There was evidence that the reduction of Cr(vi) leads to insoluble Cr reduction products on the surface of the steel. Sparging of nitric acid by NO and/or NO2 caused the reduction of any Cr(vi) species present in the solution, to Cr(iii) in a few minutes. However, with no Cr(vi) present, the effect of continuous purging with NO and/or NO2 was to increase the steel corrosion rate when compared with Ar purged solutions, due to catalysis of nitrate reduction by the NOx. The conversion of Cr(iii) to Cr(vi) by nitric acid was shown to require high concentrations of nitric acid, high temperatures and low partial pressures of NO2 over the liquid phase.     

Determination of pitting initiation of duplex stainless steel using potentiostatic pulse technique

Duplex stainless steel simultaneously comprises various phases, inclusions, precipitates and grain boundaries. It is full of academic and valuable significance for materials designing and processing optimization to ascertain the corrosion resistance of corresponding phases and various microstructures. However, up to date, efficient evaluation technique is still scare mainly due to difficulty in controlling of micropits. In this work, for the first time, optimized potentiostatic pulse technique (PPT) was established and applied to study the rule of initiation of pits of solution annealed and aged DSS in 1.0 mol/L NaCl solution. The results showed that the size of pits can be well-controlled by adjusting the condition of potential pulse. Combined with SEM/EDS system observation, it was found that for solution-annealed specimens, sulphide and oxide mixed inclusions were the preferential pit initiation sites, while for aged specimens, majority pits occurred at inclusions in area impoverished in Cr/Mo, which is vicinal to σ phase. The phenomena that growing pits is retarded by precipitation rich in Cr/Mo, i.e. σ phase, was testified and explained.     

Polybithiophene and its bilayers with polyaniline coatings on stainless steel by electropolymerization in aqueous medium

For the first time, electrosynthesis of polybithiophene (PBTh) and its bilayers with polyaniline (PAni) coatings on stainless steel (SS) in aqueous oxalic acid solutions containing monomer and sodium dodecyl sulfate (SDS) was carried out by potentiodynamic synthesis technique. Smooth and adherent films were obtained on the steel surfaces. Homopolymers and bilayers were characterized by cyclic voltammetry, FTIR, UV–vis spectroscopies and SEM. Homopolymers were also characterized by means of conductivity and the number average molecular weight measurements. The effects of the scanning potential limits on electrosynthesis of PBTh and its bilayer coatings were investigated. The test for corrosion protection of the polymer coated and uncoated SS substrates were performed in highly aggressive 0.5 M NaCl and 0.5 M HCl solutions by linear potentiodynamic polarization and Tafel test technique, respectively. Corrosion test revealed that among the protective coatings obtained, PBTh as homopolymer and PAni/PBTh as bilayer exhibited the most effective anticorrosive properties. According to linear potendynamic polarization test, the dissolution current of these coatings at 1.6 V decreased to 99.8% and 99.6% in NaCl solution, respectively, when compared to that of uncoated SS surfaces.     

MIC of stainless steel in freshwater and the cathodic behaviour of biomineralized Mn-oxides

Microbially influenced corrosion by manganese oxidizing microorganisms (MIC by MOMOs) is a corrosion phenomenon occurring in freshwater systems affecting stainless steels. Typically, chloride induced corrosion is observed at chloride concentrations normally not considered as critical. The initiation of corrosion is attributed to an anodic shift of the open circuit potential of the passive stainless steel caused by manganese dioxide biomineralized by the specific organisms. However, not only the potential of the passive steel seems of interest. For the stabilization of localized corrosion, the ability of the cathodic reaction to drive enough current for promoting the switch from metastable pitting to stable pit growth is considered important. Consequently, experiments have been carried out in order to compare the dynamic cathodic properties of the usual oxygen reduction reaction with that of biofilm incorporating biomineralized MnO₂. The results indicate a significantly better cathodic performance of such biofilm which might explain the fast and extensive damages observed in certain cases of MIC by MOMOs.     

The corrosion resistance of 316L stainless steel coated with a silane hybrid nanocomposite coating

The present work aims at evaluating the corrosion resistance of 316L stainless steel pre-treated with an organic–inorganic silane hybrid coating. The latter was prepared via a sol–gel process using 3-glycidoxypropyl-trimethoxysilane as a precursor and bisphenol A as a cross-linking agent. The corrosion resistance of the pre-treated substrates was evaluated by neutral salt spray tests, linear sweep voltammetry and electrochemical impedance spectroscopy techniques during immersion in a 3.5% NaCl solution. In addition, the effect of the drying method as an effective parameter on the microscopic features of the hybrid coatings was studied using Fourier transform infrared spectroscopy and scanning electron microscopy. Results show that the silane hybrid coatings provide a good coverage and an additional corrosion protection of the 316L substrate.     

Corrosion initiation of stainless steel in HCl solution studied using electrochemical noise and in-situ atomic force microscope

An in-situ atomic force microscope (AFM), optical microscope and electrochemical noise (ECN) techniques were applied to the investigation of corrosion initiations in an early stage of 1Cr18Ni9Ti stainless steel immersed in 0.5 M HCl solution. The electrochemical current noise data has been analyzed using discrete wavelet transform (DWT). For the first time, the origin of wavelet coefficients is discussed based on the correlation between the evolution of the energy distribution plot (EDP) of wavelet coefficients and topographic changes. It is found that the occurrence of initiation of metastable pitting at susceptive sites is resulted from the reductive breakdown of passive film of stainless steel in the diluted HCL solution. The coefficients d₄-d₆ are originated from metastable pitting, d₇ represents the formation and growth of stable pitting while d₈ corresponds to the general corrosion.     

Electrochemical corrosion characteristics of type 316 stainless steel in simulated anode environment for PEMFC

The corrosion behavior of type 316 stainless steel in simulated anode environment for proton exchange membrane fuel cell (PEMFC), i.e., dilute hydrochloric acid solutions bubbled with pure hydrogen gas at 80 °C, was investigated by using electrochemical measurement techniques. The main purpose is to offer some fundamental information for the use of stainless steels as bipolar plate material for PEMFC. Both polarization curve and electrochemical impedance spectroscopy (EIS) measurements illustrate that 316 stainless steel cannot passivate spontaneously in the simulated environments. The absorbed (and/or adsorbed) hydrogen atoms from cathodic corrosion reactions on the steel surface may deteriorate the passivity and corrosion resistance. The oxidation of these hydrogen atoms gives rise to a second current peak in the anodic polarization curve, and the current increases with immersion time. EIS spectra also reveal that a porous corrosion product layer formed on the steel surface during the active dissolution in the test solutions. 316 stainless steel exhibits the similar corrosion behavior in sulfate ions containing dilute hydrochloric acid solution.     

The corrosion-inhibiting effect of polypyrrole films doped with p-toluene-sulfonate,benzene-sulfonate or dodecyl-sulfate anions,as coating on stainless steel in NaCl aqueous solutions

This article presents a study of the conditions for electro-synthesis of polypyrrole (PPy) films on stainless steel, in the presence of the anions p-toluene-sulfonate (pTS), benzene-sulfonate (BS) or dodecyl-sulfate (DS). Cyclic voltammetry (CV) was used in the synthesis of the polypyrrole films on the stainless steel (SS). These polymeric films were characterized by IR and UV–vis spectroscopy and their morphology and thickness were analyzed by scanning electron microscopy (SEM). Their performance as protective films against corrosive processes presented by the SS/PPy-pTS, SS/PPy-BS or SS/PPy-DS systems was evaluated in 0.1 M NaCl aqueous solution. The study of the corrosion processes of the stainless steel/polymer systems was conducted through measurements of open circuit potential (E_OCP), polarization curves (PC) and electrochemical impedance spectroscopy (EIS). The results showed that the protective capacity of these polymeric systems on stainless steel, mainly with regard to pitting, depends on the nature of the anion dopant used during electro-synthesis of the PPy film. The best performance was seen with the dopants pTS and BS.