A novel method for the preparation of thin dense Pd membrane on macroporous stainless steel tube filter

Thin Pd membranes were in situ deposited on macroporous stainless steel (MPSS) tubes using an improved electroless plating method consisting of material filling in the substrate pores, Pd plating on the filled substrate, and recovery and activation of the substrate pores. The Pd/MPSS composite membranes resulted from the filling materials of both aluminum hydroxide gel and Pd/aluminum hydroxide gel have been studied in detail and compared with each other. The hydrogen permeation mechanism through both membranes may be controlled by surface reactions, while the hydrogen permeation flux and activation energy for the membrane resulted from Pd/aluminum hydroxide gel are higher than these for the membrane resulted from aluminum hydroxide gel. In the case of the former membrane, which is almost pinhole free, the hydrogen permeation flux is as high as 0.302 mol/(m² s) with a pressure difference of 100 kPa at 773 K. Good membrane stability is also proven by the unchanged membrane surface morphology, the steady hydrogen permeance, and the complete hydrogen selectivity. The deposition mechanism of the membrane has been proposed and interpreted in detail.     

Preparation and thermal treatment of Pd/Ag composite membrane on a porous alumina tube by sequential electroless plating technique for H2 separation

Pd/Ag/α-Al2O3 composite membranes were prepared by sequential electroless plating technique. The prepared membranes were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, energy dispersive spectroscopy, and inductively coupled plasma atomic emission spectroscopy techniques （ICP-AES）. Effects of annealing time, Ag content, and air treatment on the hydrogen permeation flux and morphology of the alloys were investigated. The results of the investigation showed that the prepared type of tube had a good potential as substrate for membrane preparation. In addition, a uniform defect-free alloy was prepared by annealing at 550 ℃ in H2 atmosphere. The permeation results showed an increase in H2 permeation flux by increasing the Ag content and the annealing time. In addition, the air treatment of the prepared membranes at 400 ℃ for 1 h changed the morphology of the alloy and substantially enhanced the hydrogen flux.     

Thin Pd membrane on α-Al2O3 hollow fiber substrate without any interlayer by electroless plating combined with embedding Pd catalyst in polymer template

Palladium acetate and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) were dissolved in chloroform to form a homogeneous solution. Using this solution, thin polymer template film with embedded Pd catalyst was coated on a porous α-Al₂O₃ hollow fiber substrate. The Pd in the template film was used as the catalyst for electroless plating of Pd membranes. After the template was removed by heat treatment, the thin Pd membranes without any intermediate layers and substrate penetration were synthesized successfully. The as-synthesized Pd composite membranes of thickness less than 5 μm not only have a very high hydrogen permeance/permeability but also have a good hydrogen selectivity. Moreover, the good membrane stability was verified by the long-term operation under the condition of hydrogen permeation and the gas exchange cycles between pure hydrogen and pure helium. The good membrane stability was interpreted by estimating the shear stress of the special membrane configuration with small gap between Pd membrane and porous substrate layer.     

An observation of palladium membrane formation on a porous stainless steel substrate by electroless deposition

The membranes made of palladium and its alloys are used for the extraction of high quality hydrogen from a mixture of gases. Most of recent research is focused on the development technologies for depositing a durable ultra-thin palladium membrane on a porous substrate in order to assure a good mechanical support and maximize the flux of hydrogen permeation. The formation of a palladium membrane deposited on a porous stainless steel substrate by an electroless process is recorded and described in this paper. The palladium deposition progress around the pore area at the surface of the substrate in the initial stages is illustrated. A bridge model is presented to describe the membrane formation around the pore area of the substrate. This model, together with the micrographs showing the deposition progress on the pore areas, will lead to the control of the deposition process for a membrane fabrication as well as the design and modification of a substrate.     

Optimum cleaning-in-place conditions for stainless steel microfiltration membrane fouled by terephthalic acid solids

Terephthalic acid (TPA) is a raw material of polyester fiber and polyethylene terephthalate. When TPA is produced by catalytic air oxidation of p-xylene in the presence of acetic acid solvent, most of produced TPA exists in the form of crystalline suspended solids. A microfiltration process may be used to recover TPA, but the microfilters are subjected to fouling and therefore cleaning-in-place (CIP) regimes need to be developed. In this research, the effects of variations to CIP conditions were investigated on the flux recovery accomplished in a TiO₂-sintered stainless steel microfiltration membrane (0.1 μm pore size) fouled with TPA. The extent of flux recovery was estimated as the ratio of the stabilized flux obtained during CIP to the water flux value achieved under corresponding operational conditions. Based upon batch solubility tests, sodium hydroxide (NaOH) was chosen as the major cleaning agent for the present experiment. The extent of flux recovery increased with increasing NaOH concentration over the range of 3–4% (w/v) NaOH, but decreased at NaOH concentrations above 4%. The flux recovery was favored at high cross-flow velocities, high temperatures and low transmembrane pressures. A high temperature run of cleaning did not produce any adverse effects up to 70 °C. The addition of surfactants (SDS and Tween 80) to the caustic cleaning agent led to a significant reduction in cleaning efficiency.     

Hydrogen evolution reaction and formic acid oxidation by decorated nanostructural Pt/Pd on a copper-filled nanoporous stainless steel

In this work, a 304 stainless steel (SS) was anodized to prepare nanoporous SS (NPSS) with an average size of about 75 nm and then filled with copper (Cu/NPSS) using pulsed electrodeposition method. Afterward, a nanostructural Pt and Pd film was deposited by galvanic replacement (GR) on the Cu/NPSS to prepare modified electrode (PtPd/Cu/NPSS) for hydrogen evolution reaction (HER) and formic acid electrooxidation (FAO). The electrocatalytic activity of the modified electrode and its structural characterization have been studied by voltammetric methods, electrochemical impedance spectroscopy (EIS), inductively coupled plasma optical emission spectrometry (ICP-OES), and field emission scanning electron microscopy (FESEM). The results show that the nanostructural Pt₁Pd₁/Cu/NPSS composition, with low Pt loading and suitable stability, has a good electrocatalytic performance toward HER (E_Onset = + 12 mV vs. NHE) and FAO (E_Onset = ?180 mV vs. NHE). For HER observed a high mass activity of noble metals (87.54 mA cm^?2μg _Pd+Pt ^?1 ) in comparison with Pt deposited Cu/NPSS (41.5 mA cm^?2 μg _Pt ^?1 ) at the same applied potential of ? 0.25 V versus NHE. Also, the fabricated electrocatalysts with more electrochemically active surface area in comparison with Pd/Cu/NPSS and Pt/Cu/NPSS revealed more resisting to the poisoning components and good stability for FAO.     

Ti/(Ti,Cr)N/CrN multilayer coated 316L stainless steel by arc ion plating as bipolar plates for proton exchange membrane fuel cells

Arc ion plating(AIP) is applied to form Ti/(Ti,Cr)N/Cr N multilayer coating on the surface of 316 L stainless steel(SS316L) as bipolar plates for proton exchange membrane fuel cells(PEMFCs). The characterizations of the coating are analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Interfacial contact resistance(ICR) between the coated sample and carbon paper is 4.9 m cm~2 under 150 N/cm~2,which is much lower than that of the SS316 L substrate. Potentiodynamic and potentiostatic tests are performed in the simulated PEMFC working conditions to investigate the corrosion behaviors of the coated sample. Superior anticorrosion performance is observed for the coated sample, whose corrosion current density is 0.12 μA/cm2. Surface morphology results after corrosion tests indicate that the substrate is well protected by the multilayer coating. Performances of the single cell with the multilayer coated SS316 L bipolar plate are improved significantly compared with that of the cell with the uncoated SS316 L bipolar plate, presenting a great potential for PEMFC application.     

Characteristics of Pd/Nafion electrodes prepared by an impregnation-reduction method in sensing hydrogen

The influences of reductant concentration and Pd loading on the response and recovery times and the sensitivity in detecting hydrogen of Pd/Nafion electrodes prepared by an impregnation-reduction method were investigated in this study. The Pd/Nafion electrodes with a Pd loading of 6.90 mg/cm², obtained at 0.006 M Pd(NH₃)₄Cl₂ and 0.06 M NaBH₄, show the maximum sensitivity of 0.0519 μA/ppm in the H₂ concentration range 0–4410 ppm. However, The Pd/Nafion electrodes with a Pd loading of 11.42 mg/cm², obtained at 0.01 M Pd(NH₃)₄Cl₂ and 0.06 M NaBH₄, show the fastest response and recovery speed in sensing hydrogen. Generally, the response time decreases with an increase of the hydrogen concentration, but the recovery time increases with an increase of the hydrogen concentration. A sensing model is also proposed to illustrate the sensing phenomenon. Electronic Publication     

Preparation of a palladium alloy composite membrane supported in a porous stainless steel by vacuum electrodeposition

Pinhole-free palladium/nickel (Pd/Ni) alloy membranes deposited on a porous stainless steel (SUS) support have been fabricated. The deposition was made by vacuum electrodeposition technique which could produce the alloy film less than 1 μm thick. This technique allows for the Pd/Ni alloy by employing Pd/Ni complex reagent, and typical Pd/Ni plating had compositions of 78% Pd and 22% Ni. In order to make the surface smooth and enhance the adhesive bond between the top layer and the substrate, a nascent porous SUS disk was treated sequently with submicron nickel powder and CuCN solution. The important parameters that can affect deposition were pore size, defects, and surface roughness of substrate. The membranes were characterized by permeation experiments with hydrogen and nitrogen at temperatures ranging from 623 to 823 K and pressures from 10.3 to 51.7 cmHg. The composite membranes prepared in this technique yielded excellent separation performance for hydrogen: hydrogen permeance of 5.79×10⁻² cm³/cm² cmHg s and hydrogen/nitrogen (H₂/N₂) selectivity was 4700 at 823 K.     

Electrocrystallization of palladium from Pd(NH3)4Cl2 bath on stainless steel 316L

Electrochemical deposition of palladium from 0.04 M Pd(NH₃)₄Cl₂, NH₄Cl, and NH₄OH bath (pH = 10) on stainless steel electrode was studied by voltammetry, chronopotentiometry, and chronoamperometry. Crossovers in cyclic voltammograms demonstrate that the deposition of palladium proceed via a nucleation/growth mechanism. Chronopotentiograms indicate that palladium reduction is not controlled by diffusion and Sand’s law is not obeyed. In the early stage of the deposition, two-dimensional (2D) nucleation and growth proceeding through instantaneous and a multitude of progressive steps followed the initial double layer charging. The processes are manifested as broad maxima in chronoamperogram and after which the current transient terminates to a plateau. Non-linear fitting methods were applied to obtain the kinetic parameters in the light of Bewick, Fleischmann, and Thirsk theory for 2D and Armstrong, Fleischmann, and Thirsk model for 3D nucleation and growth process.     

A chromium(III) oxide-coated steel wire prepared by arc ion plating for use in solid-phase microextraction of aromatic hydrocarbons

The authors introduce an arc ion plating method for the deposition of chromium oxide (Cr₂O₃) on a steel wire substrate, and its use as a coating for solid phase microextraction. The coating has a micro- and nano-scaled structure after annealing at 700 °C. It is found that Cr₂O₃ exhibits a good extraction capability for the aromatic hydrocarbons naphthalene, anthracene, fluorene, fluoranthene, and biphenyl. Following desorption by high temperature at 300 °C, the analytes were quantified by gas chromatography (GC). The limits of detection are in the range between 20 and 200 ng·L^?1, and calibration plots are linear within a wide range (0.2 to 400 μg·L^?1). The coating has excellent mechanical properties, with a hardness is as high as 31.7 GPa, and the adhesion strength between coating and substrate reaches 20.1 N (corresponding to the critical Hertzian contact stress of 10 GPa). This, along with the chemical and thermal stability of the Cr₂O₃ coating, endows the wire with a long operational life. It was used for at least 100 times without any obvious decline of extraction capability.

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Graphical abstract An arc ion plating method was introduced for the deposition of chromium oxide (Cr₂O₃) on a steel wire substrate, and its use as a coating for solid phase microextraction with high mechanical strength, stability, and long operational lifetime.

     

Pitting inhibition of stainless steel by surfactants: an electrochemical and surface chemical approach

Pitting corrosion of stainless steels causes tremendous damage in terms of material loss and resulting accidents. Organic surfactants have been tried as pitting inhibitors but the understanding of the inhibition mechanisms is mainly speculative. In the present study the inhibition of the pitting corrosion of 304 stainless steel by N-lauroylsarcosine sodium salt (NLS) in 0.1 M NaCl solutions at neutral pH was studied using an approach that combines surface chemical techniques with electrochemical ones. It was found that NLS increases the pitting resistance of 304 stainless steel, with possible complete inhibition at high NLS concentration (30 mM). Adsorption of NLS on 304 stainless steel particles was directly measured. NLS adsorbs significantly on 304 stainless steel with maximum adsorption density close to bilayer coverage. Electrophoretic mobility data for 304 stainless steel particles show that the surface of 304 stainless steel is negative in NaCl solution at neutral pH. The adsorption of NLS makes the interfacial charge even more negative. The relationship between pitting inhibition and adsorption density of NLS suggests that NLS does not adsorb preferentially on the pit nucleation sites and complete inhibition requires that the whole surface be covered completely by NLS. The inhibition mechanism of NLS is proposed to be due mainly to the blocking effect of a negatively charged NLS adsorption layer. This study shows that in addition to the adsorption amount of surfactant, interfacial charge also plays an important role in pitting inhibition.     

Large area mapping of non-metallic inclusions in stainless steel by an automated system based on laser ablation

Large area compositional mapping (>6 mm²) using a fast and automated system based on laser-induced plasma spectrometry is presented. The second harmonic of a flat top Nd:YAG laser beam was used to generate a microline plasma on the sample surface. The emitted light from the microline plasma was imaged onto the entrance slit of an imaging spectrograph and was detected by an intensified charge-coupled device to generate a spatially and spectrally resolved data set. Individual LIPS images, each measuring roughly 2500×2500 μm with spatial resolution of 50 μm between adjacent craters and 4.8 μm along the microline are presented. These large area maps were acquired in less than 1 min. Steel samples containing MnS and TiN inclusions were chosen as the most adequate for this study. The results are presented for the characterization of inclusionary material in stainless steel products in terms of morphology, distribution and abundance.     

Preparation of an efficient nanofiltration membrane based on blending of polysulfone and polysulfone-g-butylacrylate prepared by ATRP

Polysulfone is one of the most common used polymers for preparation of nanofiltration membranes. These membranes are highly susceptible to fouling problems because of their surface hydrophobic nature. In this paper a new approach for modification of polysulfone to overcome the fouling problems was introduced. The modification was carried out via blending of polysulfone with a modified grafted polysulfone using atom transfer radical polymerization (ATRP) method. The modified grafted polysulfone was synthesized via ATRP grafting of n-butylacrylate from chloromethylated polysulfone. The graft copolymers were characterized by FT-IR, NMR, DSG and TGA techniques. Furthermore, surface morphology and performance of the corresponding membrane were studied in detail using SEM and pure water flux and salt rejection experiments, respectively. The results indicated that the prepared modified polysulfone membranes have high surface hydrophilicity and therefore better fouling resistance and very good water permeability.     

乙二胺改性聚氯乙烯大孔螯合树脂富集分离微量金, 铂, 钯, 铱的性能和机理研究

本文利用ICP化学光谱法对自合成的聚乙烯乙二胺大孔螯合树脂富集分离微量金, 铂, 钯, 铱进行了研究, 讨论了螯合树脂对各微量元素的富集性能、吸附速率和富集机理, 并进行了样品的分析, 获得了较满意的结果。     

Determination of trace nitrite ion in water by spectrophotometric method after preconcentration on an organic solvent-soluble membrane filter

A simple and rapid preconcentration technique, based on collecting trace nitrite on a membrane filter and dissolving the membrane filter in an organic solvent, has been applied to its spectrophotometric determination in water. At pH 2.0, nitrous acid diazotizes with p-aminoacetophenone. which is then coupled with N-(1-naphthyl)ethylenediamine, at the same pH. The azo dye formed is collected on a 0.45 urn nitrocellulose filter at pH 4.7 as its ion associate with dodecyl sulfate. The ion associate and filter are dissolved in a small volume of 2-methoxyethanol (methylcellosolve), and acidized with 0.05 ml of 2 M hydrochloric acid and the absorbance of the resulting solution is measured at 555 nm against a reagent blank. Detection limits better than O.1 mug/dm(-3) as NO(2)(-) can be achieved. The ions normally present in water do not interfere when sodium metaphosphate is added as a masking agent. The proposed method has been applied to the analysis of water samples from several sources, the recoveries of the nitrite added to the samples are quantitative, and results found are satisfactory.     

Depth profile analyses by GDOS on stainless steel surfaces after exposure to liquid lithium

Summary Depth profile analyses by means of glow discharge optical spectroscopy (GDOS) has been performed on stainless steel SS 316 samples after 3 different modes of exposure in liquid lithium at 600° C. The figures represent the qualitative correlation between element concentration (intensity, arbitrary units) and the sputtered depth (sputtertime, seconds). Differences in depletion and enrichment of certain elements amongst others, have been attributed to the differences of the impurities, namely N and C in lithium.

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Tiefenprofilanalyse an in flüssigem Lithium ausgelagerten Stahlproben mittels Glow Discharge Optical Spectroscopy (GDOS)

Zusammenfassung Es wird über die Tiefenprofilanalyse mittels Glow Discharge Optical Spectroscopy an rostfreiem Stahl SS 316 nach 3 unterschiedlichen Auslagerungen in flüssigem Lithium bei 600° C berichtet. In den Kurven wird qualitativ der Zusammenhang zwischen der Konzentration der Elemente (Intensität in Volt in willkürlichen Einheiten) in Abhängigkeit von der Abtragtiefe (in Sekunden-Sputterzeit) dargestellt. Die Unterschiede in der Anbzw. Abreicherung einzelner Elemente konnten außer der unterschiedlichen Auslagerung, auch auf die Verunreinigungen im Li, insbesondere N und C zurückgeführt werden.

     

A biofilm resistance surface yielded by grafting of antimicrobial peptides on stainless steel surface

Anti‐biofilm formation on the surface is a severe issue in medical implants, hull surface, and food industry. Antimicrobial peptide, magainin II, was covalently bound to stainless steel surfaces through multi‐step modification. The untreated and modified samples were analyzed by SEM‐EDS, XPS, and contact angle, respectively, which indicated the peptide was immobilized on the surfaces. The antimicrobial tests of modified samples were conducted using Staphylococcus aureus and Escherichia coli, and the results revealed that peptide modified surface decreased the biofilm and bacteria quantity of stainless steel surface.     

Influence of bath temperatures on the wettability of copper films surface prepared by electroless plating method on beech wood

Copper films were coated on beech wood substrates by electroless plating method. The influence of bath temperature on the copper films properties was studied by varying the bath temperatures 25, 35, 45 and 55 °C. Scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) pattern, X‐ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and contact angle measurements were used to both characterize the physical and chemical copper films properties and understand the influence of bath temperature on the wettability of copper surface. In our studies, we have found that the gained copper mass significantly increased at 55 °C. The crystalline nature of the coated copper was confirmed by XRD. The presence of Cu₂O and CuO was observed by XPS and micro Raman techniques, which confirms the oxidization of the coated copper surface. Also these characterization techniques have shown the big influence of bath temperature on the morphology, grain size, chemical composition and the film thickness of the coated copper. The wettability was highly influenced by increasing CuO on the coated copper, which is increased by the bath temperature. The contact angle measurements have demonstrated the influence of C―O, O―C?O and CuO components of the surface on the wettability of the samples. Copyright © 2016 John Wiley & Sons, Ltd.