Studies of the adsorption of oligomers and surfactants on carbon and steel surfaces in a hydrocarbon medium

The adsorption isotherms for an (amino) terminally functionalised, oligomeric polyisobutylene and for a series of alkylpropoxylate or alkylbutoxylate surfactant molecules on carbon particles, in isooctane, have been obtained. The isotherms on carbon show that the oligomer is the most strongly adsorbing species. The surfactants show some evidence of forming aggregates on the carbon surface at higher concentrations. Analysis of the adsorption isotherms indicate that the size of these aggregates is similar on the carbon particles and on steel balls, reported previously, but that in some cases the actual adsorbed amounts on the two surfaces differ considerably. Ellipsometric studies carried out in situ on steel surfaces in isooctane show that only the polymer gives a relatively thick adsorbed layer. Addition of surfactant reduces the adsorption of the oligomer. There are some differences between the thickness values reported previously using AFM, compared to those found in the current work using ellipsometry, but in both cases it would seem that some degree of multilayer adsorption is occurring for the oligomer on steel in isooctane.     

Dilatometric model for determining the formation of austenite during continuous heating in medium carbon steel

Journal of Thermal Analysis and Calorimetry - A model was developed to predict the formation of austenite and dilatometric behavior during continuous heating in AISI 1045 steel, which has an...     

The inhibitory effect of bipyridine and its cobalt complex on the corrosion behaviour of carbon steel in acidic medium

The bipyridine (bipy) and its cobalt complex (Co-bipy) were tested as corrosion inhibitors for N80 carbon steel in 0.1 M H₂SO₄ solution by electrochemical polarization and electrochemical impedance spectroscopy (EIS) method. Scanning electron microscopy (SEM) techniques were used to characterize the mild steel surface. The test results showed that the complex and ligand are mixed-type inhibitors and the compounds are adsorbed on the steel surface according to Temkin adsorption isotherm. The inhibition efficiency of the inhibitors follows the trend Co-bipy > bipy. The adsorption of the inhibitors can be classifies as physical adsorption.     

The use of naphthidine as indicator in the determination of zinc in metallurgical analysis

Using naphthidine as an internal indicator in the titration of zinc with standard potassium ferrocyanide solutions, suitable procedures are recommended for the determination of zinc in various non-ferrous alloys and in rubber ashes. With aluminium alloys, aluminium bronzes and white metals the zinc is separated from interfering elements by hydrogen sulphide procedures, whereas with tin bronzes the separation is best accomplished by an 8-hydroxyquinoline procedure. After the solution of rubber ashes in hydrochloric acid, the major interfering elements are removed from the zinc by filtration after making the solution ammoniacal. With samples giving large precipitates with ammonia, it is necessary to redissolve them and determine the entrained traces of zinc.     

Corrosion inhibition investigations of 3-acetylpyridine semicarbazone on carbon steel in hydrochloric acid medium

The corrosion inhibition efficiency of 3-acetylpyridine-semicarbazide (3APSC) on carbon steel (CS) in 1.0 M HCl solution has been investigated using weight loss measurements, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization studies. The results show that inhibition efficiency on metal increases with the inhibitor concentration. 3APSC exhibited marked inhibition towards carbon steel in HCl medium even at low concentrations. The adsorption of inhibitor on the surfaces of the corroding metal obeys the Langmiur isotherm and thermodynamic parameters (K _ads, ?G _ads ⁰ ) were calculated. Activation parameters of the corrosion process (E _a, ?H* and ?S*) were also calculated from the corrosion rates. Polarization studies revealed that 3APSC act as a mixed-type inhibitor. Surface analysis of the metal specimens was performed by scanning electron microscopy.     

The possible way to evaluate the purity of double-walled carbon nanotubes over single wall carbon nanotubes by chemical doping

Here, we carried out Raman study on chemically doped single wall carbon nanotube (SWNT)/double-walled carbon nanotube (DWNT) mixed bucky-papers. Their highly different Raman responses (e.g., a large upshift of tangential mode of SWNT and no large changes in the frequencies of tangential mode assigned to the outer tubes of the DWNT) upon doping with the sulfuric acid could be used as a qualitative indicator of the purity of the DWNT samples with the concentration of its SWNTs contents.     

The use of Monte Carlo simulations to evaluate kinetic data and analytic approximations

Experimental kineticists are always faced with the problem of reducing kinetic data to extract physically meaningful information. A particularly vexing problem arises when different models reproduce the data but yield different values for the physical parameters. For over forty-five years Monte Carlo simulation techniques have been used to study the statistical behavior of parameters extracted from data. Not only do these simulations provide realistic uncertainties, correlation coefficients, and confidence envelopes, but they also provide insight into the nature of the model. These insights may be obtained by viewing two-dimensional scatter plots of the fractional changes of the parameters and one-dimensional histograms of the distributions of the changes in the parameters. Monte Carlo simulations are illustrated with examples from OH+CH₄ → CH₃+H₂O and the high-pressure rate coefficient for methyl-methyl association. A more complex problem involves models for pressure-dependent rate coefficients in the falloff region. We have modeled methyl-methyl association with five of the most current analytic approximations for behavior in the falloff region. All of these reproduce the data to within their uncertainties. However, when Monte Carlo techniques are applied the correlations between the parameters and the nonlinear nature of their behavior become evident. We postulate that the statistical behavior of the parameters of a model may be used to distinguish one model from another and, thereby, identify those analytic approximations that hold promise for further investigation and utilization. Finally, the recent advent of high-speed workstations implies that Monte Carlo simulations should become a routine part of the analysis of kinetic data. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 803–817, 1997     

Influence of aminodiester on steel hydrogenation in a hydrosulfuric medium

The influence of N-(2-carboethoxyethene)-N-(2-carbobuthoxyethyl)methylamine on the process of hydrogen penetration in steel (St.3) in a hydrosulfuric medium was studied.     

Determination of bismuth in metallurgical materials using a quartz tube atomizer with tungsten coil and flow injection-hydride-generation atomic absorption spectrometry

A method for the determination of bismuth in metallurgical materials using hydride generation coupled with a merging zones flow system and atomic absorption spectrometry using a quartz tube atomizer with tungsten coil is proposed. The parameters related to the bismuthine generation, the flow injection system and the use of a tungsten coil were studied and the optimized system shows a wide calibration range and good stability over time, without losses in sensitivity. The analytical curve is linear from 10 to 750 μg l⁻¹ of Bi with R0.999. A detection limit of 1.9 ng Bi and an analytical frequency of 60 determinations per hour were obtained. Five metallurgical reference materials were analyzed with the proposed method after their acid dissolution. The results obtained were in good agreement with certified or recommended values, and the relative standard deviations were lower than 5%.     

The use of solution microcalorimetry to evaluate chemically modified fish scales as a viable adsorbent for heavy metals

Here, we report for the first time the direct and simultaneous determination of kinetic and energetic parameters of Cr(VI) sorption on chemically modified fish scales (GA-scale) using solution microcalorimetry. Characterization has suggested that electrostatic interactions between scales collagen positive charges and chromate negative charges constitute the majority of the interactions. The microcalorimetric kinetic data of Cr(VI) sorption on GA-scale were successful adjusted to a three-parameter exponential function. The enthalpies of Cr(VI) sorption on GA-scale are highly exothermic (from −226.43 to −183.79 kJ mol⁻¹), and Cr(VI) interaction energies decrease as initial Cr(VI) in solution increases. The kinetic and thermodynamic from solution microcalorimetry results suggest that the interactions GA-scale/Cr(VI) occur mainly by surface reactions. The maximum adsorption capacity of GA-scale for Cr(VI) was found to be comparable with some commercial adsorbent samples.     

An investigation of carbon steel corrosion inhibition in hydrochloric acid medium by an environmentally friendly green inhibitor

The inhibition effect of polyphenols extracted from olive mill wastewater (PP) on carbon steel in 1.0 M HCl solution was studied. Inhibition efficiency of PP was carried out by using chemical (weight loss method) and electrochemical techniques [potentiodynamic polarization and electrochemical impedance spectroscopy (EIS)]. The effect of temperature and immersion time on the corrosion behavior of carbon steel in 1.0 M HCl with addition of an extract was also studied. The results show that PP acts as a very good inhibitor, and the inhibition efficiency increases with the concentration of PP and decreases with rising temperature. Polarization curves show that PP behaves as a mixed-type inhibitor in hydrochloric acid. Data, obtained from EIS measurements, were analyzed to model the corrosion inhibition process through an appropriate equivalent circuit model; a constant phase element has been used. EIS shows that charge-transfer resistance increases and the capacitance of double layer decreases with the inhibitor concentration, confirming the adsorption process mechanism. The activation energy as well as other thermodynamic parameters for the inhibition process were calculated. The adsorption of PP obeys the Langmuir adsorption isotherm.     

The role of the medium in electrochemical functionalization and dispersion of carbon nanotubes

An electrochemical method for dispersion of single-walled carbon nanotubes (SWNTs) is described. The technique is based on grafting of oxygen-containing functional groups to the nanotube surface during electrolysis in aqueous and nonaqueous potassium bromide solutions. A dependence of the degree of functionalization of nanotubes on the solvent was revealed experimentally. Nanotubes treated in DMSO have about 14 carbon atoms per oxygen atom from functional groups (cf. nearly four C atoms per oxygen atom in the nanotubes treated in aqueous solutions). The corresponding maximum specific capacities of the electrodes are nearly 10 and 60 F g⁻¹. The samples treated in solutions of KBr in DMSO have about 300 carbon atoms per bromine atom on the nanotube surface (cf. only 30 carbon atoms in the samples treated in aqueous solution). A mechanism of electrochemical modification of SWNTs is proposed. Its key step is production of atomic oxygen that oxidizes the nanotube surface with the formation of functional groups.     

The use of carbon fiber for the irradiation position of a fast-rabbit system

Contamination of rabbits with activities induced in the metal parts live of an irradiation facility constitute a major source of problems for INAA using short-lived nuclides. If the half life of the nuclides of interest is longer than about 10 sec, it is possible to unpack the sample without appreciable loss of information. But for shorter half lives, automatic unloading devices for rabbits have to be used. Such systems are complicated and can not be used for cyclic activation procedures. At IRI, a fast rabbit system is being installed consisting of polyethylene tubing and a carbonfiber end point at the core position. Carbonfiber combines a good mechanical stability under in-core conditions with a very high purity. It can be expected that as a result of the use of this material, contamination by the rabbit will become negligible, so that samples can be counted directly without unpacking. Results obtained with this new system are presented, and compared with results obtained with an aluminium rabbit system used until now.     

Correlation of NMR and UV results to evaluate the stability constants of carbon tetrachloride complexes

An equation has been suggested which correlate the NMR and UV results to evaluate the stability constant of electron donor acceptor complexes. Using this equation the stability constant of complexation between carbon tetrachloride and hexamethylbenzene has been studied by UV and NMR spectroscopy.     

The use of microcalorimetry to assess the size exclusion properties of carbon molecular sieves

Carbon molecular sieves (CMSs) for separating gaseous mixtures have been prepared through chemical vapour deposition (CVD) of benzene on activated carbon fibres (ACFs) obtained from Nomex aramid fibres. The effect of the CVD treatment on the porous texture of the ACFs has been followed by immersion calorimetry into liquids of different molecular sizes (dichloromethane, benzene and cyclohexane). Both the kinetics of the immersion process and the equilibrium immersion enthalpies have been studied. Besides, the derived specific surface areas accessible to the different liquids employed have been calculated. The results show that the carbon deposition has taken place mainly at the pore entrances and the CVD treatment has succeeded to introduce selectivity without a significant loss of capacity.     

The use of stable carbon isotope analysis to detect the abuse of testosterone in cattle.

The use of stable carbon isotope analysis to detect the administration of anabolic steroids to cattle was investigated. Samples were extracted by solid-phase extraction on C18 cartridges. Stable isotope ratios (13C:12C) were measured by gas chromatography-isotope ratio mass spectrometry (GC-IRMS) of the underivatised extracts. A programmed temperature vaporiser (PTV) injector was installed in the GC-IRMS system, which conferred a number of advantages. First, it allowed large volumes of sample to be injected whilst the injector liner was cool. The solvent was subsequently vented to the atmosphere prior to transfer of the sample to the GC column. Thus a significantly greater amount of sample could be presented for analysis, thereby increasing the sensitivity. Second, by this means virtually all the solvent could be removed prior to analysis. This eliminates solvent peak tailing, which can be a major problem in GC-IRMS. Finally, the PTV allowed the use of higher initial GC oven temperatures, which in turn facilitated the analysis of underivatised steroids by reducing the GC run time and improving the chromatographic peak shape. The carbon isotope composition of 5 beta-androstane-3 alpha,17 alpha-diol, the major metabolite of testosterone found in bovine bile, was measured in bile samples from untreated cattle and from cattle injected intramuscularly with testosterone or a mixture of testosterone esters. There was considerable inter-animal variation in the values obtained and there was no significant difference between samples from treated and untreated animals. However, when the isotopic composition of the metabolite was normalised with respect to that of an endogenous reference compound (cholesterol) in the same sample, the difference between treated and untreated animals become statistically significant.     

The use of doped crystals as a medium for the study of excited state bimolecular interactions

A molecular crystal is an attractive medium for the study of excited state intenmolecular interactions since the ground state positions of interacting molecules may be accurately determined. Besides excimer interactions in pure crystals it is possible to study (in doped crystals) exciplex interactions between host and guest molecules, and even excimer formation between two adjacent guest molecules. This approach has been utilized to observe excimer formation by several anthracene derivatives introduced as dopants in pyrene crystals. Photochemical reactions of some of these exciplexes and excimers are discussed. Excimer forming crystals are considered to be good candidates for excited state structure determination by means of pulsed x-ray diffraction.     

Relations between the aspect ratio of carbon nanotubes and the formation of percolation networks in biodegradable polylactide/carbon nanotube composites

The biodegradable polylactide composites containing carbon nanotubes (CNTs) with high aspect ratio (HAR) and low aspect ratio (LAR) were prepared by melt mixing. The physical properties of those two systems were characterized in terms of rheology, conductivity, and mechanical properties for establishing preliminary structure–property relations. Several viscoelastic models were then used to further describe the relations between aspect ratio and percolation network of CNTs. The results show that these two CNTs present different structural characteristics in the polylactide (PLA) matrix during melt mixing: the LAR CNTs are far stiffer than the HAR CNTs. At low loading levels, the former is dispersed as bent fibers or their small bundles, whereas the latter is dispersed as self‐entangled flocs, presenting far larger hydrodynamic radius than the former. At high loading levels, both are dispersed as flocs due to strong tube–tube interactions. However, the two CNTs show approximate average floc size and mesh size because they present same rigid length and effective aspect ratio. At identical loadings, therefore, the HAR CNTs have more total number of flocs than that of the LAR CNTs, forming network with more compact structure and imparting higher contributions to properties of the composites as a result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 479–489, 2010