Effect of aluminum on the corrosion resistance of low-alloy steel in 10wt% sulfuric acid solution

The aqueous corrosion behavior of low-alloy steel with aluminum contents was examined in a 10 wt% H₂SO₄ (pH 0.13) solution using electrochemical techniques and surface analyses. The corrosion resistance of the new alloy steel was evaluated in terms of electrochemical parameters, such as passive current density, film, and charge transfer resistances. The results showed that a high Al content in the steel imparted better passivation behavior resulting in a lower corrosion rate. It related to the enrichment of iron carbonate and hydrocarbon by the dissolution of the carbide phase.

Hydraulic performance of geosynthetic clay liners to sulfuric acid solutions

The ability of geosynthetic clay liners (GCLs) to contain acidic mining leachates is examined. The results of saturated hydraulic conductivity (k) of two GCLs permeated with sulfuric acid solutions (H2SO4) at 0.015M, 0.125M and 0.5M concentrations are reported. Also, the saturated k values of consolidated (35kPa) bentonite cakes made from sodium bentonite extracted from both GCLs were compared to a commonly used magnesium-sodium form bentonite. Chemical compatibility and effects of pre-hydration and effective stress were assessed as part of this study. Results indicated that an increased acid concentration (ionic strength) increased the k of all tested specimens. The ratio of the k0.5 values for non-prehydrated specimens permeated with 0.5M H2SO4 to the kw values for specimens permeated with deionized (DI) water (k0.5/kw) ranged from 10 to 110. Pre-hydration (50-140% water content) and increased effective stress (35-200kPa) improved the performance of GCLs (lower k). Strong correlations were observed between k and liquid limit and swell index parameters independent of pre-hydration and effective stress in this study. However, care should still be taken when using these correlations to evaluate hydraulic performance because the intrinsic micro-structure properties of bentonite, such as porosity, should also be considered. This work showed that, for example, high SI of bentonite does not translate necessarily to a better hydraulic performance of GCLs.

Synergistic corrosion inhibition of mild steel in aqueous chloride solutions by an imidazolinium carboxylate salt

Mild steel infrastructure is constantly under corrosive attack in most environmental and industrial conditions. There is an ongoing search for environmentally friendly, highly effective inhibitor compounds that can provide a protective action in situations ranging from the marine environment to oil and gas pipelines. In this work an organic salt comprising a protic imidazolinium cation and a 4-hydroxycinnamate anion has been shown to produce a synergistic corrosion inhibition effect for mild steel in 0.01 M NaCl aqueous solutions under acidic, neutral, and basic conditions; an important and unusual phenomenon for one compound to support inhibition across a range of pH conditions. Significantly, the individual components of this compound do not inhibit as effectively at equivalent concentrations, particularly at pH 2. Immersion studies show the efficacy of these inhibitors in stifling corrosion as observed from optical, SEM, and profilometry experiments. The mechanism of inhibition appears to be dominated by anodic behavior where dissolution of the steel, and in particular the pitting process, is stifled. FTIR spectroscopy provides confirmation of a protective interfacial layer, with the observation of interactions between the steel surface and 4-hydroxycinnamate.

Chemistry, spectroscopy and analytical applications of certain chemiluminescent reactions

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

Enhanced thermal properties and morphology of ion-exchanged polypyrrole films

The thermal stability of electrochemically prepared polypyrrole (PPy) films with p-toluenesulfonate (pTS) or perchlorate (ClO₄⁻) counterion (PPy/pTS and PPy/ClO₄⁻) is improved by simple treatment with aqueous sulfuric acid, sodium sulfate or sodium bisulfate. The degree of stabilization achieved depends on the solution, temperature and duration of treatment. Although the mechanism for improved stability is not yet clear, it is apparent that the level of ion exchange and the original polymer microstructure are important. A model for the conductivity decay as a function of thickness has been proposed. The early stages of ion exchange are not symmetrical, and diffusion is facilitated at the electrode side of the film. Furthermore, X-ray diffraction shows no evidence of morphological change after treatment of PPy/pTS (43 μm), but in PPy/pTS (12 μm) and PPy/ClO₄⁻ (41 μm) films an additional peak is indicative of more ordered structure following treatment. The glass transition temperature, T_g, of PPy/pTS and PPy/ClO₄⁻ films obtained by modulated differential scanning calorimetry is approximately 155°C.

Ion exchange, anisotropic structure and thermal stability of polypyrrole films

The thermal stability of electrochemically prepared polypyrrole (PPy) films with p-toluene sulfonate (pTS) or perchlorate (CIOP₄⁻) counter ion (PPy/pTS and PPy/ClO₄⁻) is improved by simple treatment with aqueous sulfuric acid, sodium sulfate or sodium bisulfate. The degree of stabilization achieved depends on the solution, temperature and duration of treatment. PPy/pTS is easily stabilized and thick films (43μm) retain 90 % of the initial conductivity after long period (300 h) at 150 °C, while thinner films (12 μm) retain slightly less (70 %). A model for the conductivity decay has been proposed. Although the mechanism for improved stability is not yet clear it is apparent that the level of ion exchange and the original polymer microstructure are important. The early stages of ion exchange are not symmetrical and diffusion is facilitated at the electrode side of the film. Furthermore, X-ray diffraction shows no evidence of morphological change after treatment of thick PPy/pTS but in thin PPy/pTS and PPy/ClO₄⁻ films an additional peak is indicative of more ordered structure following treatment. These observation may imply that there is a higher density of crosslinks and branching at the growth side than at the electrode side of the film.

Homogeneous isolation of nanocelluloses by controlling the shearing force and pressure in microenvironment

Nanocelluloses were prepared from sugarcane bagasse celluloses by dynamic high pressure microfluidization (DHPM), aiming at achieving a homogeneous isolation through the controlling of shearing force and pressure within a microenvironment. In the DHPM process, the homogeneous cellulose solution passed through chambers at a higher pressure in fewer cycles, compared with the high pressure homogenization (HPH) process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) demonstrated that entangled network structures of celluloses were well dispersed in the microenvironment, which provided proper shearing forces and pressure to fracture the hydrogen bonds. Gel permeation chromatography (GPC), CP/MAS 13C NMR and Fourier transform infrared spectroscopy (FT-IR) measurements suggested that intra-molecular hydrogen bonds were maintained. These nanocelluloses of smaller particle size, good dispersion and lower thermal stability will have great potential to be applied in electronics devices, electrochemistry, medicine, and package and printing industry. © 2014 Elsevier Ltd.

Forces between mica surfaces in ethylene glycol

Measurements are presented of the force as a function of separation between two molecularly smooth mica surfaces immersed in ethylene glycol, and in solutions of lithium chloride and sulfuric acid in ethylene glycol. At surface separations greater than 3 nm the measured force is in very good agreement with double-layer theory, but at smaller separations there is an oscillatory solvation force which is superimposed on the double-layer repulsion. In contrast to the case in water, the adsorption of hydrogen ions at the mica surface does not markedly affect the short-range forces.

The behaviour of praseodymium 4-hydroxycinnamate as an inhibitor for carbon dioxide corrosion and oxygen corrosion of steel in NaCl solutions

Praseodymium 4-hydroxycinnamate (Pr(4OHCin)3) was investigated as a novel corrosion inhibitor for steel in NaCl solutions, and found to be effective at inhibiting corrosion in both CO2-containing and naturally-aerated systems. Surface analysis results suggest that the corrosion inhibition ability of Pr(4OHCin)3 in the naturally-aerated corrosion system could be attributed to the formation of a continuous protective film. For the CO2-containing system, the corrosion inhibition efficiency of Pr(4OHCin)3 was predominantly because of formation of protective inhibiting deposits at the active electrochemical corrosion sites, in addition to a thinner surface film deposit. © 2013.

Synthesis and anti-corrosion performance of Adenine-L-Alanine ramification

In this paper, a new amino acid derivative, namely Adenine-L-Alanine ramification (ALAR) was synthesized and investigated as a green corrosion inhibitor for X80 pipeline steel in 0.1 mol/L hydrochloric acid solution using the weight loss, AC impedance, and polarization curve method. The structure of the derivative was characterized by IR and UV–vis spectrum. The weight loss and AC impedance found that the inhibition efficiency increased with the increase in concentration of the inhibitor but decreased with rise in temperature, the corrosion inhibition efficiency attains 91.26% in 8 × 10−2 g/L concentration at 30 °C. The polarization studies showed that the studied amino acid derivative can be used as a corrosion inhibitor. The surface of inhibited and uninhibited specimens was analyzed by scanning electron microscopy and the adsorption of the inhibitor on the mild steel surface obeys Langmuir adsorption isotherm. The quantum chemical descriptors such as the energy of highest occupied molecular orbital, energy of lowest unoccupied molecular orbital were calculated and the inhibition mechanism can be analyzed by the distribution of electrons. Analysis indicated that the inhibitor molecular and empty d orbital of metal forms the coordination bond, covers on the surface of metal, and prevents corrosion reaction.