Fundamental issues of the effective decontamination of the steam generators of Paks NPP</p> </p>

Summary During the period of 1993-2001 chemical decontaminations of 24 SGs in the units 1-3 of the Paks NPP were carried out by a non-regenerative version of AP-CITROX technology, even in two or three consecutive cycles. A comprehensive investigation of the above decontamination method have revealed that the fundamental issues of analytical chemistry and corrosion science were not taken into consideration during the elaboration of AP-CITROX procedure. Therefore, the non-regenerative version of the technology utilized at Paks NPP can be considered to be not an adequate method for the chemical decontamination of any reactor equipments having large steel surfaces (e.g., SGs). As a consequence of the lack of the appropriate decontamination method, initiation of a R&D project focused on the elaboration of the required technology should not be postponed. In this paper, we present a brief overview on the fundamental issues of the technology development. Selected findings obtained in our laboratory on the field of the improvement of the AP-CITROX technology are also reviewed in order to demonstrate the crucial role of some selection criteria.</p> </p>     

Hydrodynamics of the effectiveness of the AP-CITROX decontamination technology

During the optimization of the AP-CITROX decontamination technology the effect of the different flow rates of the decontamination solutions on the radioactive contamination and corrosion state of stainless steel tube samples originating from steam generators of Paks NPP were studied by a pilot-plant circulation system. The results have proved that a significant increase (up to 2.89 m/s) in the flow rate of the decontamination solution in the 1-5 steps is highly recommended and in order to improve the passivity of the surfaces it should be kept as low as possible (0.5 m/s) during the passivation.     

Optimization study on sample pretreatment of spent fuel storage rack

In order to evaluate radionuclide inventories as an essential item for the permanent disposal of spent fuel storage racks, chemical conditions for a sample pretreatment of a spent fuel storage rack were studied. Especially, the surface microstructure and the radionuclide distributions for the spent fuel storage rack were investigated by using a SEM–EDX and γ-spectrometer for minimizing the matrix effect which could affect a chemical separation process of some β-emitting radionuclides. The samples were pretreated with a mixed solution of 5 M HCl and 2 M HNO₃ by an ultrasonic surface leaching method. Some radionuclides in the raw racks showed the radioactivity of 10²–10³ Bq for about 10 g of sample weight. From the sample pretreatment, it was confirmed that almost all radionuclides in the rack were completely extracted from the rack when the dissolved thickness of the rack became a maximum 15 μm by the ultrasonic surface leaching method. The established pretreatment method was applied for all spent fuel storage rack generated from Korean NPPs to determine the scaling factor. The radioactivities of ⁶⁰Co and ¹³⁷Cs radionuclides in the pretreated solutions were in the range of 4.9E−1~1.5E+2 and 1.2E−1~9.0E+0 Bq/g, respectively.     

Non-equilibrium potentiometry—the very essence

In most interpretations of potentiometric ion sensor responses with glass, solid, or liquid/polymer membranes, a model assuming electrochemical equilibrium between the aqueous sample and the membrane is used. This model is often called a phase boundary model to emphasize the importance of ion-exchange processes at the interface. The essence of the phase boundary model is that it accepts electroneutrality and thermodynamic equilibrium, and thus ignores electrochemical migration and the time-dependent effects. For this reason, this model is in conflict with many experimental reports on ion sensors in which both kinetic (time-dependent) discrimination of ions to improve selectivity and non-equilibrium transmembrane ion transport for lowering the detection limits are deliberately used. To respond to the experimental challenges in the author’s groups, we elevated the potentiometric modeling by using the Nernst–Planck–Poisson (NPP) equations system to model the non-equilibrium response. In the NPP model, electroneutrality and steady-state/equilibrium assumptions are abandoned, and thus we access the space and time domain. This approach describes the concentration changes of ions participating in the ion-exchange and transport processes, as well as the electrical potential evolution over space and time, and allows in particular, the inspection of the equilibrium set by the phase boundary models as a special “stationary” case after infinite time. Additionally, directly predicting the selectivity and the low detection limit variability over time and the influence of other parameters, e.g., ion diffusibility, is possible. As a coherent and non-arbitral model, the NPP system facilitates solving the inverse problem, i.e., to optimize the sensor properties and measurement conditions in a customized way via desired target functions and hierarchical genetical strategy modeling. In this way the NPP allows setting the conditions under which the experimentally measured selectivity coefficients are true (unbiased) and the detection limits are optimized.     

Effects of AP-CITROX Decontamination Procedure on the Surface Oxide Layer Composition of Stainless Steel Originating from the Primary Circuit of a VVER-Type Nuclear Reactor

A real specimen originating from the primary circuit of a VVER-440 type pressurized water cooled nuclear reactor has been studied by Conversion Electron Mössbauer Spectroscopy (CEMS) in order to find out how the AP-CITROX decontamination procedure modifies the structure and composition of the surface oxide layer of stainless steel which is used in the steam generator. Other methods like voltammetry, gravimetry, and SEM-EDAX were also applied to characterize the samples and to help the interpretation of CEMS results. It was found that, in contradiction with expectations, the presence of the surface magnetite layer could not be convincingly identified even on the non-decontaminated sample. This finding together with the relatively weak Mössbauer signals indicated that the surface oxide layer is strongly Fe-depleted. It was also concluded that the upper layer of the bulk steel (under the oxide layer) has an altered composition probably due to irradiation-enhanced diffusion of the metallic constituents. It was established that the AP-CITROX decontamination procedure does not exert detrimental effects on the thickness and composition of the surface oxide layer.     

Hydrophobic siloxane paper coatings: the effect of increasing methyl substitution

Paper is an organic material widely used in cultural heritage and mainly composed of cellulose mixed with lignin, hemicellulose and small amounts of additives. This paper deals with siloxane coatings on pure cellulose paper, applied by sol–gel dipping in sols prepared with different siloxane precursors (tetraethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane, trimethyl monoethoxysilane). The coated samples were characterized using various techniques (Fourier Transform Infrared Spectroscopy FT-IR, Nuclear Magnetic Resonance NMR and Scanning Electron Microscopy and Energy Dispersive Spectroscopy SEM–EDS), measuring their mechanical properties, flame resistance and contact angles, and a colorimetric test. The coated samples’ behavior was more hydrophobic the higher the methyl number of siloxane precursor, regardless of the coating’s thickness. Increasing the thickness improved the mechanical and thermal properties. The thickest coatings were obtained using a double coating process and a basic catalyst for the hydrolysis step, but this latter condition facilitated the formation of surface agglomerates, which make the paper too stiff and yellow.     

Electrochemical deposition and corrosion stability of Zn–Co alloys

Electrochemically deposited Zn–Co alloys under various deposition conditions were investigated using anodic linear sweep voltammetry for phase structure determination, scanning electron microscopy for surface morphology analysis, atomic absorption spectroscopy for determination of chemical composition, and polarization measurements and open circuit potential measurements for determination of corrosion properties. The influence of deposition current density, temperature, and composition of deposition solution on the phase structure and corrosion properties of Zn–Co alloys was studied. It was shown that the ratio of cobalt to zinc ions in the plating bath strongly affects the chemical content and phase structure, as well as corrosion stability, of Zn–Co alloys. Zn–Co alloys deposited from plating baths with the lowest and the highest ratios of cobalt and zinc ions exhibited the lowest corrosion rate.     

Effect of carbon nanotubes’ crystal structure on adsorption kinetics of small molecules An experimental study utilizing ultra-high vacuum thermal analysis techniques

The effect of carbon nanotubes’ (CNT) crystal structure on chemical reactivity has been studied in much detail in the liquid phase using CNT suspension. This type of information is pertinent for developing CNT separation strategies. However, few experimental studies are available providing data for gas–CNT interactions utilizing ultra-high vacuum (UHV) surface science techniques. Structure–activity relationships (SAR) for gas–surface interactions are important for sensor designs and heterogeneous catalysis exploring, for example, CNT’s potential as a support for fuel cell catalysts. We report on UHV kinetics experiments with single-wall metallic, semiconducting, and mixed CNTs in order to provide the experimental basis to correlate CNT’s crystal structure and chemical activity. Thermal desorption spectroscopy (TDS), a simple temperature ramping technique, has been used to determine the binding energies of a number of probe molecules including alkanes, alcohols, thiophene, benzene, and water on CNTs at UHV conditions. TDS allows for the identification of adsorption sites of probe molecules in CNT bundles, using gold foil or silica as a support for the drop-and-dry technique. A weak and probe molecule dependent SAR is present for adsorption inside the CNTs but not for the population of external sites by the probe molecules. The experimental data are in part consistent with current theoretical predictions by other groups. In addition, the effect of different solvents (methanol, SDS, and NMP) and cleaning procedures will briefly be discussed using results of spectroscopic (Auger electron spectroscopy) and kinetic techniques. Furthermore, molecular beam scattering techniques were utilized to characterize the adsorption dynamics, i.e., the gas-to-surface energy transfer processes of alkanes on CNTs. For example, opening the CNT tube ends by high temperature annealing, increases the so-called initial adsorption probability, that is, the probability for adsorption in the limit of zero surface concentration (coverage). This result directly illustrates the effect of large surface areas of CNTs, using internal and external surfaces, for gas adsorption.     

Host (nanocavity of zeolite Y)/guest (Co(II), Ni(II) and Cu(II) complexes of unsaturated 16-membered octaaza; 3,4,11,12-tetramethyl-1,2,5,6,9,10,13,14-octaazacyclohexadecane; Me4[16]aneN8 nanocomposite materials (HGNM): template synthesis, characterization and catalytic oxidation of benzyl alcohol

Nanocavity zeolite-Y (host) encapsulated Co(II), Ni(II) and Cu(II) complexes of unsaturated 16-membered octaaza; 3,4,11,12-tetramethyl-1,2,5,6,9,10,13,14-octaazacyclohexadecane ‘Me₄[16]aneN₈’; macrocycle (guest) were synthesized and characterized by chemical analyses, s.e.m., x.r.d., u.v.–vis., d.r.s., surface area, pore volume, conductometric, magnetic measurements and i.r. spectroscopy with a view to confirming the encapsulation of complexes and to arrive at the composition, structure and geometry of encapsulated complexes. The characterization data show the absence of extraneous complexes, retention of zeolite crystaline structure and encapsulation in the nanocavities. Host–Guest Nanocomposite Materials (HGNM) ‘[M(Me₄[16]aneN₈)]²⁺-NaY’ are catalytically very efficient as compared to other neat complexes for the partial oxidation of benzyl alcohol which is stable and becomes recycled without much deterioration.     

Chemical dissolution of iron in aqueous solutions

By anodic oxidation of hydrogen on the Pt ring of a metal-disk-Pt-ring rotating electrode in aqueous acid (pH 0.5–3) sulfate solutions, it is shown that during the polarization of the metal disk hydrogen coevolves by two parallel reactions. One is the well known electrochemical charge transfer process, while the other one is a direct chemical reaction of the metal, i.e. iron, with water molecules from the electrolyte. This process was proposed a long time ago by Kolotyrkin and co-workers, but their experimental results were subjected to serious criticism which is taken care of in the present paper. The chemical reaction is potential- and pH-independent and, depending on the actual conditions during the corrosion processes (actual potential, pH, etc.), can be of greater or smaller importance in the overall process. The consequences of the existence of this direct chemical reaction of metal with water molecules (i.e. H₂O-induced corrosion or chemical corrosion) on pitting and stress corrosion cracking of metals is discussed. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the authors in English.     

Some problems with determination of alpha-active nuclides during decommissioning of nuclear power plant A-1

The first step in decommissioning of NPP is connected with defueling and successful disposal of liquid radioactive wastes (LRW), both from previous production and all work connected with this step. These require precise knowledge about the concentration of radioactive nuclides presented, especially alpha-emitters in all material fluxes arising in sich work (namely shut-down after some accident). This paper reports, results of the determination of U, Pu, Am and Cm by means of both the commonly used and the newly developed radiochemical procedures in various types of materials, e.g., LRW, aerosol filters, ashes resulted from incineration technology, metal surfaces, decontamination solutions etc.     

Nanocomposite solar cells: the requirement and challenge of kinetic charge separation

Nanocrystalline solar cells promise significant advantages with respect to cost-efficient mass production, since they do not require imprinted chemical potential gradients for charge separation (e.g., electrical fields generated by p, n doping, which should last for one to three decades). They, however, require kinetic charge separation and chemical electronic mechanisms, which rectify photocurrents for energy conversion. Such mechanisms are presently not well understood, since the existing nanosolar cells (dye and polymer solar cells) have evolved largely empirically. It is shown in this paper that function and properties of kinetically determined solar cells can be derived from irreversible thermodynamic principles considering minimum entropy production (or the principle of least action) and involve solid-state electrochemical processes. Based on this model, presently studied nanosolar cells and also the primary photosynthetic mechanism are analyzed to identify the most significant physical–chemical factors involved. Dedicated to the 85th birthday of John O’M. Bockris. Parts of this contribution were previously reported as a lecture at QUANTSOL 2008, Bad Gastein, Austria, March 2–7, and at NANOMAT 2008, Ankara, Turkey.     

Effects of exposure time on the anodic dissolution of Monel-400 in aerated stagnant sodium chloride solutions

The anodic dissolution of Monel-400 (63.0% Ni, 28–34% Cu) alloy after its immersion in freely aerated stagnant 3.5% NaCl solutions for 0, 24, and 72 h has been investigated. The study was carried out using a variety of electrochemical techniques and gravimetric measurements after varied exposure periods (5–160 days). The work was complemented by scanning electron microscopy and energy dispersive X-ray analyzer (SEM/EDX) investigations. The electrochemical measurements showed that Monel suffers both general and pitting corrosion. The severity of uniform corrosion decreased, while pitting one increased with increasing the immersion time to 24 h and further to 72 h before measurements. Gravimetric data indicated that the weight loss increased, while the corrosion rate decreased for Monel with time. SEM images and EDX profile analyses confirmed that the corrosion of Monel after 160 days immersion in NaCl solutions occurs due to the selective dissolution of nickel.     

Aerosol-assisted synthesis of mesoporous titania nanoparticles with high surface area and controllable phase composition

Mesoporous titania nanoparticles (denoted as MTN) with high surface area (e.g., 252 m² g⁻¹) were prepared using tetrapropyl orthotitanate (TPOT) as a titania precursor and 10–20 nm or 20–30 nm silica colloids as templates. Co-assembly of TPOT and silica colloids in an aerosol-assisted process and immediate calcination at 450 °C resulted in anatase/silica composite nanoparticles. Subsequent removal of the silica colloids from the composite by NaOH solution created mesopores in the TiO₂ nanoparticles with pore size corresponding to that of silica colloids. Effects of silica colloids’ contents on MTN porosity and crystallites’ growth at a higher calcination temperature (e.g., 1000 °C) were investigated. Silica colloids suppressed the growth of TiO₂ crystallites during calcination at a higher calcination temperature and controllable contents of the silica colloids in precursor solution resulted in various atomic ratios of anatase to rutile in the calcinated materials. The mesostructure and crystalline structure of these titania materials were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA)-thermo-gravimetric analysis (TGA), and N₂ sorption.     

Surface treatment of zinc by Schiff’s bases and its corrosion study

The zinc metal surface is chemically modified by newly synthesized Schiff’s bases and its corrosion protection is investigated. The influence of concentration of Schiff’s bases on modification of zinc surface and immersion time in treatment bath are investigated and optimized for maximum corrosion protection efficiency. The electrochemical studies of treated zinc specimens are performed in aqueous acid solution using galvanostatic polarization technique. The treated zinc samples show good corrosion resistance. The recorded electrochemical data of chemically treated samples indicate a basic modification of the zinc surface. The protection efficiency of organic layer formed on zinc surface is tested by varying the acid concentration and temperature of the corrosive medium. The corrosion protection efficiency increases with the concentration of Schiff’s bases and immersion time. This is due to a strong interaction between zinc and the organic molecules, which results in the formation of a protective layer. This layer prevents the contact of aggressive medium with the zinc surface. The surface modification is confirmed by the scanning electron microscopy images. The interaction between metal atoms and Schiff’s bases is also established by IR studies. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 886–892. The text was submitted by the authors in English.     

Effect of the structure ofα-substituted styrenes on their electronic structure

The relationship between the experimental ionization potentials and energies of the highest occupied MO was analyzed for various conformations of styrene derivatives using the photoelectron spectra of a series of α-substituted styrenes and quantum chemical calculations of their electronic structure. The characteristics of the HOMO of the planar conformations correlate both with the ionization potentials and the reactivities of these molecules. Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg St., Donetsk, Ukraine 340014, Institute of Technical and Macromolecular Chemistry, Martin Luther University, Halle Wittenberg, Merseburg, Germany D-06217. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 34, No. 1, pp. 36–42, January–February, 1998.     

On the origin of Turing instability

A reaction–diffusion system consisting of one, two or three chemical species and taking place in an arbitrary number of spatial dimensions cannot exhibit Turing instability if none of the reaction steps express cross‐inhibition. A corollary of this result – obtained by elementary calculations – underlines the importance of nonlinearity in the formation of stationary structures, a kind of self‐organization on a chemical basis. Relations to global stability of reaction–diffusion systems, and results on multispecies systems are also mentioned. The statements are not restricted to mass action type models. As a by‐product, the solution of a basic inverse problem of formal kinetics is also presented which extends a previous result by Hárs and Tóth (1981) to models with arbitrary – including rational – functions as reaction rates so often occurring, e.g., in enzyme kinetics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Decontamination of chemical warfare agents using perchloroethylene–Marlowet IHF–H2O-based microemulsions: wetting and extraction properties on realistic surfaces

At the present time, considerable efforts are being made to develop new media for the decontamination of a variety of toxic compounds. In the present contribution, new microemulsions with promising properties are presented. Moreover, the decontamination of surfaces, with an emphasis on varnished metal surfaces of exterior and interior equipment, is investigated using these microemulsions. Studies of the phase behavior of the system water–perchloroethylene–IHF–2-propanol are reported and the microemulsion phases are recognized. The wetting behavior on contaminated surfaces and the extraction capabilities with respect to contaminants are essential for an efficient decontamination. Hence, suitable microemulsions are identified on the basis of these properties. The decontamination efficiency of these microemulsions is first estimated on the basis of the ability to wet typical chemical nonresistant varnished steel sheets, which are authentic model systems for real surfaces. Afterwards, promising microemulsions and, as reference, different solvents are tested with respect to their capability to solubilize sulfur-mustard agent, again using realistic surfaces contaminated with this chemical warfare agent. Several microemulsions are found, which have the desired properties.     

Biosynthesis of Silver Nanoparticles by <Emphasis Type="Italic">Geotricum</Emphasis> sp.

Nanoparticles are usually 1–100 nm in each spatial dimension considered as building blocks of the next generation of optoelectronics, electronics, and various chemical and biochemical sensors. In the synthesis of nanoparticles use of microorganisms emerges as an eco-friendly and exciting approach that reduce waste products (ultimately leading to atomically precise molecular manufacturing with zero waste); the use of nanomaterials as catalysts for greater efficiency in current manufacturing processes by minimizing or eliminating the use of toxic materials (green chemistry principles); the use of nanomaterials and nanodevices to reduce pollution (e.g. water and air filters); and the use of nanomaterials for more efficient alternative energy production (e.g. solar and fuel cells). Fungi have many advantages for nanoparticle synthesis compared with other organisms. In this study, Geotricum sp. found to successfully produce Ag nanoparticles. Geotricum sp. was grown in SDA (Sabro Dextrose Agar) medium at 25 ± 1 °C for 96 h. The mycelia were used to convert silver nitrate solution into nano-silver. Silver nanoparticles were synthesized using these fungi (Geotricum sp.) extracellularly. UV–VIS spectroscopy, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy images shows the nanoparticle formation in the medium. Energy-dispersive X-ray spectroscopy (EDX) also confirmed that silver nanoparticles in the range of 30–50 nm were synthesized extracellularly. FTIR analyses confirmed the presence of amide (I) and (II) bands of protein as capping and stabilizing agent on the surface of nanoparticles.     

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn₂₁Ni₅ phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005