Sensing of toxic metals through pH changes using a hybrid sorbent material: Concept and experimental validation

This article reports a new hybrid sorbent material that is capable of detecting trace concentration of toxic metals, such as zinc, lead, copper, nickel, etc., through pH changes only. The material is essentially a composite granular material synthesized through rapid fusion of a mixture of amorphous hydrated ferric oxide (HFO) and akermanite or calcium magnesium silicate (Ca₂MgSi₂O₇). When a water sample is rapidly passed through a mini‐column containing this hybrid material, effluent pH at the exit always remains alkaline (≈9.0) because of slow hydrolysis of akermanite and steady release of hydroxyl (OH^?) ions. This exit solution turns pink through the addition of a phenolphthalein indicator. Commonly encountered electrolytes containing sodium, calcium, chloride, and sulfate have no impact on the exit pH from the mini‐column. However, when trace concentration of a heavy metal (say lead) is present in the sample water, a considerable drop in pH (>2 units) is observed for the exiting solution. At this point, the solution turns colorless through the addition of a phenolphthalein indicator. Moreover, the change in the slope of pH, i.e., ?dpH/dBV, provides a sharp, noticeable peak for each toxic metal where BV is the bed volumes of solution fed. The technique allowed detection of zinc and lead through pH swings in synthesized samples, spiked Bethlehem City water, and also in Lehigh River water in the presence of phosphate and natural organic matter (NOM). Using a simple preconcentration technique, lower than 10 μg/l of lead was detected with a significant peak. From a mechanistic viewpoint, high sorption affinity of HFO surface sites toward toxic metal cations, ability of akermanite to maintain near‐constant alkaline pH for a prolonged period through slow hydrolysis and labile metal‐hydroxy complex formation causing dissipation of OH^? ions from the aqueous phase provide a synergy that allows detection of toxic metals at concentrations well below 100 μg/l through pH changes. Nearly all previous investigations pertaining to toxic metals sensing use metal‐selective enzymes or organic chromophores. This simple‐to‐operate technique using an inexpensive hybrid material may find widespread applications in the developing world for rapid detection of toxic metals through pH changes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Corrosion protection mechanisms of carbon steel by an epoxy resin containing indole-3 butyric acid modified clay

This work is an extension of studies into the mechanisms of corrosion protection of mild steel by an epoxy resin containing organically modified clay (Hang et al. [1]; Truc et al. [2]). In a previous study (Truc et al. [2]), it was shown that indole-3 butyric acid (IBA)-modified clay improved the corrosion performance of epoxy. In the present study, it was shown that the IBA is an anodic inhibitor and its efficiency was about 93%. Exfoliation and dispersion of the IBA-modified clay in the epoxy coating were checked by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The improvement of the corrosion performance of the epoxy coating containing IBA-modified clay by comparison with pure epoxy coating was confirmed for a low film thickness (10 μm). Local electrochemical impedance measurements performed on scratched samples revealed the inhibitive action of IBA at the carbon steel/coating interface. It was shown that the inhibitor release from the IBA-modified clay was favoured for high pH values. Thus, in neutral media, the corrosion process which induces a local increase of pH will increase the self-healing performance.     

Corrosion protection mechanisms of carbon steel by an epoxy resin containing indole-3 butyric acid modified clay

This work is an extension of studies into the mechanisms of corrosion protection of mild steel by an epoxy resin containing organically modified clay (Hang et al. [1]; Truc et al. [2]). In a previous study (Truc et al. [2]), it was shown that indole-3 butyric acid (IBA)-modified clay improved the corrosion performance of epoxy. In the present study, it was shown that the IBA is an anodic inhibitor and its efficiency was about 93%. Exfoliation and dispersion of the IBA-modified clay in the epoxy coating were checked by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The improvement of the corrosion performance of the epoxy coating containing IBA-modified clay by comparison with pure epoxy coating was confirmed for a low film thickness (10 μm). Local electrochemical impedance measurements performed on scratched samples revealed the inhibitive action of IBA at the carbon steel/coating interface. It was shown that the inhibitor release from the IBA-modified clay was favoured for high pH values. Thus, in neutral media, the corrosion process which induces a local increase of pH will increase the self-healing performance.     

The influence of electrolyte reduction potential on weld corrosion

Electrochemical potentiodynamic sweeps and galvanic studies are performed to determine conditions that will initiate localized corrosion in welded areas. The reduction potential and pH in the electrolyte seemed to be essential with respect to where corrosion attacks occur in a welded area of carbon steel. The interpretation of the polarization diagrams for the different parts of the weld showed that they actually had different anodic Tafel slopes and this interpretation could be used to make predictions concerning preferential corrosion behavior. A variance of brine composition causes a change of attacked areas in a weld.     

Adaptive Polymeric Coatings with Self‐Reporting and Self‐Healing Dual Functions from Porous Core–Shell Nanostructures

In biological system, early detection and treatment at the same moment is highly required. For synthetic materials, it is demanding to develop materials that possess self‐reporting of early damage and self‐healing simultaneously. This dual function is achieved in this work by introducing an intelligent pH‐responsive coatings based on poly(divinylbenzene)‐graft‐poly(divinylbenzene‐co‐methacrylic acid) (PDVB‐graft‐P(DVB‐co‐AA)) core–shell microspheres as smart components of the polymer coatings for corrosion protection. The key component, synthesized PDVB‐graft‐P(DVB‐co‐AA) core–shell microspheres are porous and pH responsive. The porosity allows for encapsulation of the corrosion inhibitor of benzotriazole and the fluorescent probe, coumarin. Both loading capacities can be up to about 15 wt%. The polymeric coatings doped with the synthesized microspheres can adapt immediately to the varied variation in pH value from the electrochemical corrosion reaction and release active molecules on demand onto the damaged cracks of the coatings on metal surfaces. It leads simultaneously to the dual functions of self‐healing and self‐reporting. The corrosion area can be self‐reported in 6 h, while the substrate can be protected at least for 1 month in 3.5 wt% NaCl solution. These pH‐responsive materials with self‐reporting and self‐healing dual functions are highly expected to have a bright future due to their smart, long‐lasting, recyclable, and multifunctional properties.     

Polymeric corrosion inhibitors for copper and brass pigments

Copper and brass pigments corrode in aqueous alkaline media with the absorption of oxygen that can be measured gasvolumetrically. These corrosion reactions can be inhibited by certain polymers; the metallic sparkle and the color of the pigments is preserved. The brass pigment is inhibited more effectively than the copper pigment. Some low‐molecular mass styrene–maleic acid (SMA) copolymers are efficient corrosion inhibitors; a low acid number is necessary but not sufficient for corrosion inhibition. At pH 8.5 there is a potential correlation between the acid number of the low‐molecular mass SMA and the oxygen volumes absorbed from brass pigment dispersions; oxygen volumes decrease with decreasing acid number. Furthermore, increasing copolymer addition effects an increase of corrosion inhibition. Polyacrylic acids, polyvinyl alcohols and high‐molecular mass SMA copolymers are ineffective. The most efficient group of polymers examined in this study are the styrene–acrylate copolymers because by addition of these the overall lowest volumes of oxygen were absorbed by the metal pigments. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 475–483, 2001     

Mitigation of corrosion of zinc with amylopectin: Electrochemical,adsorption, and surface studies

Carbohydrate polymers are proven to be potential green corrosion inhibitors because of their outstanding structural features and eco-friendliness. Work undertaken reflects the effectiveness of biopolymer amylopectin (AMP) as an eco-friendly green inhibitor to mitigate the deterioration of zinc in 0.1 M sulphamic acid (NH₂SO₃H). Electrochemical studies like potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) were applied for corrosion rate measurement in the absence and presence of AMP. Thermodynamic and kinetic parameters were calculated and described in detail. The results were fitted into a suitable adsorption isotherm model, and an appropriate mechanism was proposed for the corrosion inhibition process. A detailed surface morphology study was done using scanning electron microscopy (SEM), electron-dispersive X-ray (EDX), and atomic force microscopy (AFM) techniques. The inhibition efficacy of AMP increased with an increase in its concentration and temperature. Upon the addition of the inhibitor, corrosion potential shifted more towards the positive side, indicating more control of the anodic process. The adsorption of AMP over zinc conformed to the Freundlich adsorption isotherm. For the concentration of 0.1 gL⁻¹, maximum corrosion inhibition efficiency of 74% could be accomplished. Surface studies reaffirmed the adsorption of AMP on the surface of the metal. Thus, AMP turned out to be an effective green inhibitor with economic benefits.     

Multifunctional,pH‐responsive graft copolymer prepared from deproteinized natural rubber and 4‐vinylpyridine via emulsion polymerization

We investigated the synthesis of a pH‐responsive graft copolymer of natural rubber and 4‐vinylpyridine. The grafting reaction was carried out using deproteinized natural rubber (DPNR) latex, with potassium persulfate as a free radical initiator. The pH responsiveness of the graft copolymer was investigated using water swelling and contact angle measurements, and was compared with that of pure DPNR. The graft copolymer was found to become responsive in solution at a pH of around 4. Indigo carmine adsorption studies identified the Langmuir isotherm, suggesting monolayer coverage. The adsorbed indigo carmine, a model anionic drug, and carbon dots, an emerging nanosized fluorophore, could be released from the graft copolymer by lowering the pH of the solution. The graft copolymer was tested as a heavy metal adsorbent, and demonstrated selectivity to copper(II) ions. The graft copolymer of 4‐vinylpyridine and DPNR developed in this study is therefore a multifunctional, pH‐responsive material with a wide range of potential applications, including sensing and catalysis, as a biomedical material and as an adsorbent. © 2017 Society of Chemical Industry     

Catalytic Dehydration of 1,2‐Butanediol to n‐Butyraldehyde in Sub‐ and Supercritical Water

The change of the raw material basis to alternative sources, especially biomass, is advisable because of both the continuous shortage of fossile resources and the advancing change in world climate. Carbohydrates have the highest share in biomass. However, as they are overfunctionalized with chemically almost equal hydroxy groups, the high‐scale industrial use of carbohydrates is restrained. In addition, the diversity and the high amount of functional groups of carbohydrates complicate the prediction of possible reaction pathways. This is the reason why monoalcohols and polyols are used as model compounds. One interesting reaction is the dehydration of 1,2‐butanediol to n‐butyraldehyde, an important chemical intermediate. Supercritical water is an appropriate reaction medium for dehydrations because of its special physical and chemical properties. The addition of acids enhances the reaction rate but at the same time intensifies corrosion. Sulfate salts, especially zinc sulfate, can have similar positive effects without increasing the corrosion potential. The experimental results of the catalytic influence of different metal sulfate salts on the dehydration of 1,2‐butanediol to n‐butyraldehyde are presented in this paper.     

Graphitic Carbon as Durable Cathode‐Catalyst Support for PEFCs

Long‐term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon‐support corrosion. It is found that the use of graphitic carbon as cathode‐catalyst support enhances its long‐term stability in relation to non‐graphitic carbon. This is because graphitic‐carbon‐supported‐Pt (Pt/GrC) cathodes exhibit higher resistance to carbon corrosion in‐relation to non‐graphitic‐carbon‐supported‐Pt (Pt/Non‐GrC) cathodes in PEFCs during accelerated stress test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance and charge‐transfer resistance are monitored through cyclic voltammetry (CV), cell polarisation and impedance measurements, respectively. The degradation in performance of PEFC with Pt/GrC cathode is found to be around 10% after 70 h of AST as against 77% for Pt/Non‐GrC cathode. It is noteworthy that Pt/GrC cathodes can withstand even up to 100 h of AST with nominal effect on their performance. X‐ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy and cross‐sectional field‐emission scanning electron microscopy (FE‐SEM) studies before and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/GrC cathodes in relation to Pt/Non‐GrC cathodes, reflecting that graphitic carbon‐support resists carbon corrosion and helps mitigating aggregation of Pt‐particles.     

The corrosion of iron in sulphate solutions at pH = 0–2

The effects of pH and stirring rate on the kinetics and mechanism of pure iron corrosion in deaerated, argon saturated solutions at 25°C have been studied. The entire concentration of sulphate ions in the tested solutions was 2.0 M. The increase of pH in the tested range causes the change of the anodic process mechanism, which is manifested in the decrease of the Tafel anodic straight line slope from 0.06 V (pH ～ 0) through 0.04 V (pH ～ 1) to 0.03 V (pH ～ 2) and the increase of the order of reaction with respect to OH^? ion, which is 0, 1 and 2 respectively. At adequately low potentials there occurs a change (to a small degree dependent on pH) of the anodic process mechanism which corresponds to the anodic straight line slope being 0.12 V. For the hydrogen evolution reaction the cathodic Tafel slope has been found to be ?0.12 V and the order of reaction with respect to OH^? ion to be ?1. Stirring of the solution has no practical effect on either the corrosion rate or the run of the polarization curves above pH = 1. For lower pH values, at the decrease of the stirring rate there occurs the increase of the corrosion rate and the increase of the anodic and cathodic process rate which is clearly visible below the corrosion potential. The cause of this phenomenon may be the catalyzing of both electrode processes by small quantities (～ 10^?7 Ml^?1) of the H₂SO₄ reduction products. The effect of pH on the corrosion potential and current has also been found.     

钢样在磷酸钠溶液中氯离子存在的极化曲线与腐蚀曲线

<正> 分析极化曲线的特微成功地探测金属在溶液中进行的腐蚀过程.把阳极极化曲线的直线部分延长到对应静电位的电流密度以代表自发腐蚀的阳极电流密度,同样得到阴级电流密度.认为阴极极化曲线和阳极极化曲线的直线部分的延是线交点,在近似情况,可代表自发腐蚀的溶解初速度.     

Electrochemical characterisation of protective organic coatings for food packaging

A very common material for food packaging is steel, in the form of metallic containers (cans), in particular for beverage packaging. The corrosion degradation of the packaging must be carefully controlled, not only because the packaging integrity must be preserved, but also in order to avoid any significant contamination of the food or drink, compromising the flavour. In order to increase the coating performance and the food compatibility, new organic coatings are under development with very high protective properties, with the final aim to increase the shelf life of the product. An electrochemical characterisation is often used to study the protective performance of organic coatings on metal substrate for various applications. Some different coatings for food packaging were considered in the present study, including materials with different chemical composition and different pigments content. The protective properties were quantified using electrochemical impedance spectroscopy (EIS) measurements, comparing the electrochemical substrate activity with electrochemical noise (EN) and scanning Kelvin probe (SKP) measurements. The influence of mechanical deformations on the protective properties was also investigated. The results obtained on the studied coatings confirmed the validity of the electrochemical approach and showed that, in general, the coatings containing pigments (TiO₂) have better performance than clearcoats, while comparing the different polymers, epoxy–phenolic coatings have a better corrosion protection than epoxy–melamine coatings.     

Characterization of the fire environments in central offices of the telecommunications industry

Eight free burning and two sprinklered fire tests were performed with electrical cable trays and live digital switch racks in a large enclosure to simulate telecommunications central office (TCO) fires started by electrical overheating. Very‐slow‐growing (non‐flaming), slower‐growing (partially flaming) and low‐intensity‐faster‐growing (flaming) fires releasing gray‐white, gray, and black smoke, respectively, were observed in the tests. Under quiescent conditions present in the unvented enclosure fire tests for cables, very‐slow‐growing fires were detected in about 1452 s, whereas the slower‐growing fires were detected in about 222 s by commercial fire detectors. Under ventilation conditions typical of TCOs, detection times were very similar for the five types of commercial TCOs fire detectors used in the tests. The average detection times for slower‐growing fires (cable fires) and low‐intensity‐faster‐growing fires (digital switch rack fires) were 242±17% and 249±11%s respectively. The TCO procedures to reduce smoke damage from fires (on fire detection, inlet ventilation flow is turned off and exhaust flow is turned on) were found to be beneficial. The extent of smoke damage decreased significantly with an increase in the exhaust flow rate. The chloride ion mass deposition suggested that equipment recovery would be possible in the smoke environment if the cable vapor concentration could be reduced below about 3 g/m³. The metal corrosion rate was found proportional to the 0.6th power of the smoke concentration, similar to that found for the corrosion of metal surfaces exposed to aqueous solutions of HCl and HNO₃ and for acid rain with no protective layer at the surface. Sprinkler water was found to wash down the smoke deposits on the surfaces with little indication of corrosion enhancement. Copyright © 2003 John Wiley & Sons, Ltd.     

Efficiency investigations of electrochemical realkalisation treatment applied to carbonated reinforced concrete — Part 1: Sacrificial anode process

The aim of this study was to assess the efficiency of a realkalisation treatment using sacrificial anodes applied to reinforced concrete degraded by carbonation. Analytical determinations (acid/base indicators, quantitative pH, alkaline profiles, SEM and micro-Raman) together with electrochemical characterizations (rest potential, impedance, linear polarisation resistance and corrosion current densities) were performed on artificially carbonated slabs, before and after treatment (mainly 15 days, 11 weeks, 6 and 12 months). The treatment efficiency was demonstrated by an increase of pH and by an alkaline ion penetration in the concrete cover. Rest potential and corrosion current densities indicated a slight decrease of the rebar corrosion activity. Complementary Raman spectroscopy showed a change in the oxide species and SEM observations indicated that the cement matrix remained almost unchanged.     

Preparation of pH‐responsive crosslinked materials from natural rubber and poly(4‐vinylpyridine)

Stimuli‐responsive elastomers are smart materials for sensing applications. Natural rubber (NR) is a renewable elastomer with excellent elasticity and fatigue resistance. In this work, a straightforward method for the preparation of pH‐responsive crosslinked materials from NR and poly(4‐vinylpyridine) (P4VP) via free radical crosslinking reaction using benzoyl peroxide (BPO) as an initiator is described. The effects of P4VP and BPO concentrations, reaction time and reaction temperature on immobilization percentage were investigated. It was found that the immobilization percentage reached 90% when using a P4VP concentration of 150 phr and a BPO concentration of 10 phr for 24 h at 90 °C. The pH responsiveness of the crosslinked materials was studied via water swelling, water contact angle and dye release measurements. Unlike unmodified rubber, the P4VP‐crosslinked NR was found to be pH‐responsive in acidic solution. Indigo carmine adsorption studies showed the Langmuir isotherm suggesting monolayer coverage of dye on the rubber surface. The dye could also be released upon increasing the pH of solution above 4. Based on these results, the introduction of pH responsiveness to NR will lead to novel responsive rubber‐based materials that can be used in biomedical and sensing applications. © 2016 Society of Chemical Industry     

Natural Silk Film for Magnesium Protection: Hydrophobic/Hydrophilic Interaction and Self‐Healing Effect

Biodegradable implants are required in order to provide successful treatment of injuries. Temporary magnesium‐based implants with particular properties are needed in cases when it is desirable not only to maintain vital activity, but also to initiate the self‐healing process of damaged bones or tissues as well. Unfortunately, the use of magnesium alloys is limited due to the fast biodegradability of the applied material. The aim of this research is to improve the corrosion resistance of magnesium alloys by sonochemical treatment in silk solution followed by additional layer‐by‐layer deposition of natural silk on the magnesium surface. The sonication process is carried out at a frequency of 20 kHz during 5–10 min, while the duration of the silk layer deposition is 15 min. The corrosion behavior of magnesium substrates modified by natural silk layer‐by‐layer assembly is studied. Magnesium substrates sonochemically treated in silk solution demonstrate three times better corrosion resistance compared to control samples sonochemically treated in water. Additional deposition of a silk layer enhances obtained corrosion resistance by 18 times, resulting in a 54‐fold increase overall.     

7‐Azidomethoxy‐Coumarins as Profluorophores for Templated Nucleic Acid Detection

Templated nucleic acid detection is an emerging bioanalytical method that makes use of the target DNA or RNA strand to initiate a fluorogenic reaction. The Staudinger reduction holds particular promise for templated sensing of nucleic acids because the involved functional groups are highly chemoselective. Here, the azidomethoxy group, which can be removed under Staudinger conditions, is used to cage 7‐hydroxycoumarin fluorophores. Reduction by phosphines and subsequent loss of the azidomethoxy substituent induce a significant bathochromic shift of the major absorbance band in the near UV region. When excited at the appropriate wavelength, this change in the absorbance spectrum translates into a substantial fluorescence turn‐on signal. The described profluorophores are readily conjugated to amino‐modified DNAs and are rapidly uncaged by a triphenylphosphine–DNA probe under the control of a DNA template. In addition, turnover of the probes on the target strand occurs and yields substantial signal amplification.     

Treatment of wastewater containing Pb and Fe using ion‐exchange techniques

Treatment of wastewater containing lead and iron was examined using two different ion‐exchange resins namely Duolite ES 467 (containing amino‐phosphonic functional groups) and a chelating ion‐exchange resin (containing hydroxamic acid functional groups). Initially different sorption parameters such as contact time, pH, concentrations of sorbent, sorbate and chloride ion were studied. The sorption kinetics was observed to be fast and equilibrium could be reached within 30 min. Lead sorption efficiency increased with increase in pH whereas the opposite trend was observed with iron. The presence of chloride ions greatly reduced the Pb sorption efficiency in the case of Duolite ES 467. Column studies were carried out to recover Pb and Fe individually using Duolite ES 467 resin. The maximum uptake of Pb at pH 2 and 3 was observed to be 11.63 and 33.96 g dm^?3 of resin respectively. Similarly, for Fe at pH 2 and 3 the uptake was observed to be 10.07 and 6.96 g dm^?3 of resin respectively. In the presence of chloride ions, column studies were carried out using Duolite ES 467 for iron and chelating ion‐exchange resin containing hydroxamic acid functional groups for lead sorption. Hydroxamic acid resin's loading capacity remains constant for at least up to 20 cycles. Copyright © 2005 Society of Chemical Industry     

Sol–gel based layer-by-layer deposits of lanthanum cerium molybdate nanocontainers and their anticorrosive attributes

The present study focuses on the synthesis of novel lanthanum cerium molybdate (LCM) nanoparticles by sol–gel synthesis method and their use in the development of nanocontainers in an anticorrosive coating application. The obtained nanoparticles were used as core material with two different polyelectrolytic shells comprising of polypyrrole (PPY) and polyacrylic acid (PAA) or polyethyleneimine (PEI) and polystyrene sulfonate (PSS) involving the entrapment of benzotriazole (BTA) as the corrosion inhibitor using layer-by-layer (LBL) deposition method. At each step of this nanocontainer synthesis, the thickness of the layers, surface charges and the presence of the functional groups were determined by particle size, zeta potential and Fourier transform infrared spectroscopy (FTIR) analysis, respectively. The X-ray diffractograms (XRD) indicated the change in the crystallinity of the nanoparticles and nanocontainers while thermogravimetric analysis (TGA) showed the thermal degradation behavior of the nanocontainers. The morphological studies conducted using scanning electron microscopy (SEM) exhibited the formation of nanocontainers containing nanoparticles in their cores. The release of BTA from the nanocontainers was evaluated at different pH values. The anticorrosive performance of the nanocontainers was examined by incorporation of the nanoparticles and nanocontainers in a commercial epoxy coating system and to be applied on mild steel and magnesium panels by electrochemical corrosion analysis. Tafel plots demonstrated the decrease in the current density with an increase in the loading percentage of nanocontainers in the epoxy system while Bode plots confirmed the significant improvement in the corrosion protection of the mild steel and magnesium by LCM nanoparticles and nanocontainers.