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Vol 54, No 2 (2018)

Physicochemical Processes at the Interfaces

On the Electronic Mechanisms of Specific Interactions between Surfactants and a Metal Surface

Kuklin R.N., Emets V.V.

Abstract

This work considers the electronic mechanism of specific interactions between a neutral surfactant and an uncharged metal surface during an elementary adsorption event. Special attention was paid to a role of the residual electronic interactions upon the exchange of electron density between the valence adsorbate orbital and the Fermi sea of metal electrons during adsorption. This interaction was simulated by the Coulomb electron–hole interactions through a potential barrier separating the surfactant and metal-electron systems. As this task concerns the problems associated with the Fermi edge singularities, the Nozières–de Dominicis theory, which enables one to study an electron’s contribution to the energetics and kinetics of adsorption event, was used to interpret the donor–acceptor effects. The expressions of spectral characteristics of the localized electron density and tunneling time were analyzed in the context of the problem. There is a positive correlation between the surfactant adsorption parameters and the scattering phases of conductivity electrons screened in the metal by a potential field created by a hole at the valence surfactant orbital.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):153-160
pages 153-160 views

A Quantum-Chemical Study of the Adsorption of Pb Atoms on Au(111)

Rogozhnikov N.A.

Abstract

The interaction of lead atoms with a gold surface based on the cluster model of a metal surface has been investigated by the density-functional-theory (DFT) method. Geometrical and energy characteristics of these interactions have been evaluated. The adsorbed lead atom formed a strong chemical bond with gold-surface atoms. During the adsorption, there occurred a significant electron-density transfer from lead to gold. At the adsorption of a few lead atoms, flat lead nuclei tending to form a hexagonal structure were formed. The energy of adsorption of each subsequent lead atom depended insignificantly on the number of adsorbed atoms. The average effective lead atomic charge decreased with the increase of the lead quantity on the surface. The contribution of lead–lead interaction increased along with the increase in the number of lead atoms on the surface. Starting with intermediate occupancies, the contribution of lead–lead interaction to the submonolayer formation energy becomes significant. The emergence of adsorbed lead atoms on the gold surface increased the highest-occupied-molecular-orbital (HOMO) energy. This entails a decrease of the electronic work function upon the modification of a gold surface by lead.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):161-169
pages 161-169 views

Molecular and Supramolecular Structures at the Interfaces

The First Example of Electron Phototransfer with the Participation of Two-Decker Lanthanide Phthalocyaninate

Gromova G.A., Lobanov A.V., Gorbunova Y.G., Tsivadze A.Y.

Abstract

The photochemical activity of the anionic form of two-decker ytterbium and lutetium pthalocyaninates (LnPc2, Ln = Yb, Lu) is observed in the process of electron transfer to 2-methyl-1,4-naphthoquinone (MNQ). Under illumination of solutions of LnPc2 (1 × 10–5 mol/L) and MNQ (5 × 10–5 mol/L) in dimethyl formamide by light with wavelength λph > 630 nm, the anionic form of the two-decker phthalocyaninate [(Pc2–)Ln3+(Pc2–)] passes into the neutral monoradical form [(Pc2–)Ln3+(Pc)]0•. The photochemical redox process is accompanied by accumulation of the reduced form of MNQ. The observed effect is the first example of electron phototransfer with the participation of two-decker lanthanide phthalocyaninates.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):170-173
pages 170-173 views

Magnesium Octa[(4'-Benzo-15-Crown-5)-Oxy]Phthalocyaninate in Low-Molecular Hydrogels: Spectral Properties and Release under Stimulation

Goldshleger N.F., Gak V.Y., Lobach A.S., Kalashnikova I.P., Baulin V.E., Tsivadze A.Y.

Abstract

This work is dedicated to low-molecular hydrogels based on biodegradable sodium deoxycholate (SDC) and lysine hydrochloride (lys × HCl) with magnesium octa-[(4'-benzo-15-crown-5)-oxy]phthalocyaninate (Mgcr8Pc) as the active component, namely, their synthesis, spectral properties of gel-solubilized Mgcr8Pc, its release from the gel etc. Addition of Mgcr8Pc occurs both via the mixing of the components and via its diffusion from the aqueous solution into the phase of the formed SDC/lys × HCl gel. Mgcr8Pc-containing hydrogels are thermoreversible. The state of Mgcr8Pc in the SDC/lys × HCl/NaCl gel at the room temperature and in the melt is studied using spectral methods. Gel melting releases Mgcr8Pc in the form of a micelle-bound monomer. The presence of the Mgcr8Pc monomer phase in the phthalocyanine-carrying supramolecular hydrogel causes fluorescent activity of the latter.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):174-184
pages 174-184 views

New Hybrid Materials Based on Nanostructured Aluminum Oxyhydroxide and Terbium(III) Bis(Tetra-15-Crown-5-Phthalocyaninate)

Martynov A.G., Bykov A.V., Gorbunova Y.G., Khodan A.N., Tsivadze A.Y.

Abstract

A new method was developed for preparation of hybrid functional nanostructures through interaction between terbium complex with tetra-15-crown-5-phthalocyanine Tb[(15C5)4Pc]2 and the surface of highly porous nanostructured aluminum oxyhydroxids (NAOs). It was shown that immobilization of phthalocyaninate on an NAO surface may be reversible upon a sorption from the solution in chloroform, and irreversable, when the adsorption occurred on the NAO surface that was chemically modified using methyltrimethoxysilane and annealed at the temperature ranging from 500 to 1100°С (NAOM). Nanostructure and chemical properties of the obtained hybrid nanomaterials were studied with the use of different methods: scanning electron microscopy, XRD, IR and diffuse reflectance spectroscopy. The sensor properties of the obtained Tb[(15C5)4Pc]2//NAO and Tb[(15C5)4Pc]2//NAOM hybrid nanostructures were studied when they interacted with ammonia and iodine vapors. It was shown that the phthalocyaninate complex on the NAO surface was liable to reduction, while the phthalocyaninate complex on the modified NAOM surface was liable to oxidation.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):185-191
pages 185-191 views

Nanoscale and Nanostructured Materials and Coatings

Nanocomposite Protective Coatings Fabricated by Electrostatic Spray Method

Golgoon A., Aliofkhazrae M., Toorani M.

Abstract

Nowadays, powder coating can be used for many application, especially for protection against corrosive environments. Powder coating is usually done with using an electrostatic device and spraying gun. With using this method, a thin film layer is created on the surface which can play decorative or protective role. In this paper, the effect of some factors such as size of powder, charging, voltage, air flow, gun distance, charge–to-mass ratio, feed rate, coating functionality, glass transition temperature (Tg), viscosity, catalyst, temperature and curing time on the coating properties and their influence on the coating were mentioned. In recent years, nano composite polymers have been considered severely. Coating properties are improved by adding nanoparticles such as clay, SiO2, TiO2 and Al2O3 to the polymer composition. These coatings are used for reducing the gas permeability, thermal stability, optical clarity and increasing the mechanical and corrosion properties of coatings also these coatings have high mechanical properties that can be pointed to its high abrasion resistance. In this paper, the corrosion properties and the effect of adding nanoparticles on the corrosion resistance properties of powder coatings have been investigated, also the mechanical properties of powder coatings were reviwed.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):192-221
pages 192-221 views

Synthesis and Characterization of Functionally Gradient Ni-ZrO2 Composite Coating

Bostani B., Parvini Ahmadi N., Yazdani S., Arghavanian R.

Abstract

For the first time, functionally ZrO2 content graded Ni-ZrO2 composite coating has been successfully co-electrodeposited from a bath with gradually increasing stirring rate. For this, different composite coatings were electroplated in the same bath with different stirring rates to find the optimum stirring rate in which the maximum content with uniform distribution of ZrO2 particles in the coating can be achieved. To produce ZrO2 content graded Ni-ZrO2 composite coating, the stirring rate was continuously increased from 0 to optimum value. By increasing of ZrO2 particles content, the microhardness increases from interface towards the surface of the coating. The results of wear resistance measurements, Electrochemical impedance spectroscopy and potentiodynamic polarization test revealed that wear and corrosion resistances of functionally graded Ni-ZrO2 (FGNZ) is higher than that of ordinary Ni-ZrO2 (ONZ) composite coating. This result has been attributed to lower mechanical mismatch between coating and substrate in the functionally graded composite coating with respect to the uniformly distributed one.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):222-229
pages 222-229 views

An Active Corrosion Inhibition Coating of Two Pack Epoxy Polyamide System using Halloysite Nanocontainer

Bagale U.D., Desale R., Sonawane S.H., Kulkarni R.D.

Abstract

This work deals with encapsulation of corrosion inhibitor in inorganic nanocontainer and the investigation of the corrosion inhibition rate from the nanocontainer. Halloysite nanotubes were used as inorganic nanocontainer for encapsulating the active corrosion inhibitor. These cylindrical shaped halloysite nanotubes are a natural aluminosilicate, which possesses similar chemical composition as that of pure kaolin clay. The structural morphology and functional organic attachments to the halloysite nanocontainers were determined by using TEM and FTIR analysis. It is found that, halloysite nanocontainers are having external and internal lumen is in nanosize (diameter) and length up to several micrometers. A maximum benzotriazole loading up to 10% (by weight) was achieved in inorganic nanotube of 50 nm external diameters and lumen of 15 nm. The release of corrosion inhibitor was carried out for 18 h at different pH ranging from 3 to 10. The weight percent of the benzotriazole encapsulated halloysite nanocontainer was varied from 2 to 10 and then dispersed in 2K clear coat epoxy-polyamide. The self-healing anticorrosion performance of these nanocomposites coating was tested with help of electrochemical impendence spectroscopy (EIS) and Tafel plot. From Tafel plots it is found that the Icorr value decreases to 1.018E–7A/cm2 from 0.018 A/cm2, when coating was applied with 2 wt % nanocontainer.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):230-239
pages 230-239 views

New Substances, Materials and Coatings

Structural Features and Tribological Properties of Multilayer Coatings Based on Refractory Metals

Pogrebnjak A.D., Kravchenko Y.O., Bondar O.V., Zhollybekov B., Kupchishin A.I.

Abstract

A comparative analysis of the structural features and tribological properties of multilayer coatings based on refractory metal compounds has been conducted in this review. Features of formation of the electronic structure of the synthesized coatings have been discussed, and the effect of methods and conditions of deposition on changes in the physicomechanical characteristics of nanocrystalline structures based on transition metal nitrides has been shown. Dependences of antifriction properties, corrosion resistance, and thermal stability on the modulation period (Λ) and the number of bilayers in the studied multilayer coatings have been determined. A decrease in the modulation period of individual layers in a coating positively affects the oxidation resistance of the coating, while an increase in the number of interfaces between the layers slows down the diffusion of oxygen atoms deep into the coating and, thereby, increases the protective properties of the multilayer system as a whole. The effect of the droplet component in cathodic-arc coatings on corrosion development mechanisms in corrosive media has been shown. A class of multifunctional multilayer coatings with an adaptive friction mechanism, which is characterized by a change in the properties and structure during tribological tests, has been discussed separately.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):240-258
pages 240-258 views

Relaxation Behavior of Acrylic Latex Polymer Modified by Water-Soluble Dye. Freezing–Thawing Mode

Aslamazova T.R., Zolotarevskii V.I., Kotenev V.A., Lomovskaya N.Y., Lomovskoi V.A., Tsivadze A.Y.

Abstract

The relaxation behavior of a styrene–acrylic latex polymer with a glass-transition temperature of ≤5°C and polymer composites on its basis modified by an indanthrene-type water-soluble dye was analyzed using the method of dynamic mechanical relaxation spectroscopy. The change in the intensity of maximum of dissipative losses of α-relaxation and also of the μ-process is found in polymer films in the negative-temperature range as dependent on the duration and number of their preliminary freezing–thawing cycles at‒30°C taking into account the modifier concentration, which is related to the change in Young’s modulus (modulus defect). Theoretical analysis is performed involving phenomenological model concepts as to the relationship between the vibration-process frequency and Young’s modulus of the polymer material.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):259-266
pages 259-266 views

Effect of Ni–P and Phosphate Intermediate Layers on Al2O3 Coating Developed by Sol-Gel Method

Mirahmahdi H., Kalantar M.

Abstract

Sol–gel method was used for applying of alumina coating on carbon steel substrate. Alumina sol was prepared with Al-isopropoxide as a precursor material. Specimens were coated with prepared alumina sol by dip coating technique. Either a film of Ni–P or phosphated intermediate layer has been pre-deposited on the carbon steel substrate by electroless plating to improve the adherence of alumina coating. The corrosion resistance of coatings in the presence of intermediate layers was evaluated by electrochemical measurement in 3.5% NaCl solution by open-circuit potential measurement at room temperature. The abrasive wear behavior of sol–gel coated specimens was measured in high stress conditions. The results indicate that, after applying an intermediate layer of phosphate or Ni–P by electroless plating technique, the wear and corrosion resistance of alumina coating have been improved. Moreover, the phosphate intermediate layer has been associated with a higher corrosion resistance, while the intermediate layer of Ni–P is more effective to improve the hardness and wear resistance of alumina coating.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):267-273
pages 267-273 views

Influence of Type of Bath Agitation (Magnetic Stirring and Rotating Disk Cathode) on Tribological Properties of Nickel Electrodeposits

Hadipour A., Bharololoom M.E.

Abstract

In this study, nickel coatings were electrodeposited by magnet stirrer process and rotating disk cathode with a pulse power source. The surface morphology and cross-section observations were made using scanning electron microscopy and optical microscopy. The results showed that there was cauliflower morphology for all samples that were electrodeposited from a bath agitated with a magnet stirrer. On the other hand, only the nickel coating that was deposited on a rotating disk cathode at 4 A/dm2 had the cauliflower morphology. By using the rotating disk cathode process the current efficiency was decreased. Also, with increasing the current density for all samples the surface roughness was decreased. The loss of mass diagram, worn surface micrograph and friction-distance profile indicated that the wear resistance of the nickel coatings that were produced by magnet stirrer process at 2 A/dm2 and rotating disk cathode process at 4 A/dm2 were lower than the other coatings.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):274-281
pages 274-281 views

A Kinetic Model for the Boriding Kinetics of AISI D2 Steel During the Diffusion Annealing Process

Keddam M., Kulka M.

Abstract

In this work, a diffusion model was proposed to estimate the boron activation energies for FeB and Fe2B layers during the pack-boriding of AISI D2 steel at temperatures of 1223, 1253 and 1273 K for a treatment time varying between 2 and 10 h. This model considers the effect of boride incubation times during the formation of the FeB and Fe2B phases. To study the influence of diffusion annealing process on the boriding kinetics of AISI D2 steel, the mass balance equations were modified in order to follow the evolution of boride layers as a function of annealing time for the specified boriding parameters. Finally, the kinetic model was validated by a comparison of the experimental thicknesses of boride layers with the predicted ones at a temperature of 1243 K for 2, 4 and 6 h. A simple equation was then obtained for estimating the total time necessary to get a single boride layer (Fe2B) that depends on the boriding parameters and on the thickness of each boride layer prior to the diffusion annealing process.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):282-290
pages 282-290 views

Physicochemical Problems of Materials Protection

Corrosion of AD31 (AA6063) Alloy in Chloride-Containing Solutions

Kharitonov D.S., Dobryden’ I.B., Sefer B., Zharskii I.M., Claesson P.M., Kurilo I.I.

Abstract

Corrosion of AD31 (AA6063) alloy in neutral 0.05 M NaCl solutions is investigated via scanningprobe microscopy, linear-sweep voltammetry, and electrochemical-impedance spectroscopy. Al−Fe−Si−Mg intermetallic particles are determined to prevail in the structure of alloy and act as local cathodes. Intermodulation electrostatic-force-microscopy imaging shows that their Volta potential differs by 570 mV from that of the host aluminum matrix, making the alloy prone to localized corrosion. We show that the corrosion of alloy in the studied electrolyte mainly develops locally and results in pitting, with charge transfer being the limiting stage of the process. A mechanism of corrosion of the AD31 (AA6063) alloy in neutral chloride-containing solutions is proposed.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):291-300
pages 291-300 views

The Effect of Doping on the Corrosion Behavior of Quasi-Crystalline Alloys in the Al–Cu–Fe–Cr System

Chugunov D.B., Klyuchagina A.N., Meshkov L.L., Osipov A.K.

Abstract

The electrochemical behavior of five alloys of variable compositions in the Al65Cu25Fe10–хCrх system in dependence on the number of QC phases in acidic and alkaline media has been investigated by the potentiodynamic method. It has been established that the samples’ corrosion stabilities increase along with the increase of the solution pH. Higher stability was manifested by alloys with a predominant quasi-crystalline (dexagonal and icosahedral) structural component.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):301-307
pages 301-307 views

A Numerical Model of Nitriding of a Gadolinium Specimen and Its Further Destruction during Storage

Chetyrbotskii A.N., Tereshina I.S., Chetyrbotskii V.A.

Abstract

A numerical model of nitriding of an isotropic gadolinium specimen and its states during further storage under normal conditions (room temperature and atmospheric pressure) is developed. The model is implemented on the basis of the principles of thermoelasticity and mass transfer. The dynamics of distribution of nitrogen (N) and gadolinium nitride (GdN) in the specimen, which represents an additional phase formed during nitriding of the specimen, is considered. An algorithm of numerical solution of model equations is given.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):308-315
pages 308-315 views

Dissolution Behavior of Electrodeposited Ni–W Alloys

Adigüzel Z., Anik M.

Abstract

Nickel (Ni)–Tungsten (W) alloys were electrodeposited galvanostatically (at–10 mA cm–2) on copper substrate with 3 different W contents under the controlled hydrodynamic conditions and then the anodic dissolution behaviors of the alloys were observed by potentiodynamic polarization and electrochemical quartz crystal microbalance (EQCM) techniques. While the structure of the electrodeposited Ni–W alloy with low W content (15.90% W) was crystalline, that of the alloy with high W content (50.80% W) was nano-crystalline according to X-ray diffraction patterns. The increase in the W content of the electrodeposited Ni–W alloy resulted decrease at pH 3 and increase at pH 7 and 12.5 in the anodic currents of the alloy. The pH dependent dissolutions caused electrodeposited alloy surface to have W—enrichment at pH 3 and Ni—enrichment at pH 7 and 12.5. These observations indicated that the selective dissolution of Ni or W was the main mechanism in the anodic dissolution of the electrodeposited Ni–W alloys. The EQCM experiments conducted at pH 7 supported the presence of the selective dissolution mechanism that the anodic dissolution potential of W was 0.42 V lower than that of Ni in the electrodeposited Ni–W alloys.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):316-324
pages 316-324 views

Electrochemical Behavior of 316 L Stainless Steel in Alkaline Environments Containing Chloride Ion

Asgari M., Aliofkhazraei M., Olum A.R., Rad R.H., Golabadi M.

Abstract

This article intends to study corrosion of 316 L stainless steel alloy in simulated concrete environments. A composition of 0.1 M sodium hydroxide plus 0.1M potassium hydroxide with different pH (9, 11 and 13) and 0, 3 and 10 wt % sodium chloride concentration has been utilized for this manner. Potentiodynamic polarization and electrochemical impedance spectroscopy were used to study electrochemical behavior. The results of potentiodynamic polarization indicate that the formed passive layer becomes more stable and its failure takes place later as increasing pH. Electrochemical impedance test also has confirmed the obtained results and also showed that the corrosion resistance of the sample assessed over dilution time. At a solution with high alkalinity (pH 13) results showed increase in total impedance after 24 h of dilution related to passive film stabilization which did not observed in samples with lower pH. In this work, electrochemical behavior of 316 L stainless steel in alkaline environments of simulated concrete is studied with chlorine ion addition and pH adjustment.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):325-332
pages 325-332 views

Production of Annealed Cold-Sprayed 316L Stainless Steel Coatings for Biomedical Applications and Their in-vitro Corrosion Response

Dikici B., Topuz M.

Abstract

316L powders were successfully deposited onto Al5052 aluminium substrates by cold spray method. Annealing was treated on the coated samples at 250–1000°C temperatures under Ar atmosphere. The in vitro performances of the coatings have been compared with using electrochemical corrosion test technique in the simulated body fluid (SBF) at body temperature (37°C). A scanning electron microscope (SEM-EDS) and X-ray diffraction (XRD) have been used for microstructural characterization and phases identifications of the coatings, respectively. The results were shown that there are high adhesions at particle and substrate interfaces and between the particles deposited as well. Also, the increasing annealing temperature increases corrosion resistance of the cold sprayed 316L stainless steel coatings. The corrosion susceptibility of the coating annealed at 1000°C was similar that of standard 316L stainless steel implant material in Ringer’s solution. The microstructural observations revealed that corrosion starts between the inter-splat powders and continues throughout the surface not in-depth.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):333-339
pages 333-339 views

Investigation Methods for Physicochemical Systems

Field Corrosion Detection of Nuclear Materials using Electrochemical Noise Techinique

Song S., Zhao W., Wang J., Li J., Gao Z., Xia D.

Abstract

Some critical issues when applying electrochemical noise (EN) in field corrosion detection of nuclear materials are solved. In this work, a portable EN measurement system for field test is established by using Compact RIO modular instrument and zero resistance ammeter (ZRA) module. The electrode system for EN measurement is built by using platinum wire or stainless steels coated with thermal sprayed ceramic coatings as counter electrode. Two EN sensors are developed based on the electrode system mentioned above, and field corrosion detection is successfully achieved. The corrosion of stainless steel pipeline surface in nuclear power plant and internal-surface corrosion of continuous blowdown piping are successfully evaluated by the established new EN measurement system.

Protection of Metals and Physical Chemistry of Surfaces. 2018;54(2):340-346
pages 340-346 views