Epoxy paint failure in B-52 fuel tanks: Part I—Preliminary development of a model for the process

A small percentage of the protective interior topcoat in B-52 integral wing fuel tanks is failing. Two separate modes of failure are observed. On vertical surfaces, fragments of paint detached from the aluminum contain frozen in wrinkles, striations and channels. On the floor of the fuel tank, paint detached from the aluminum is flat and featureless. In this first communication, the BMS10-39 epoxy paint is structurally characterized, with emphasis on the detection of elements of chemical degradation. A preliminary model is then developed for the delamination process operative on vertical surfaces, as supported by interactions of the coating with diethylene glycol monomethyl ether (DIEGME—a fuel system deicer used in military jet fuel) in high temperature distillates from JP-8 jet fuel; and for the delamination process operative on the floor of the fuel cell based on interactions of the paint with mixtures of water and DIEGME.     

Microstructure refinement of alumina: Optimisation by gas pressure sintering process

This paper investigates densification and grain growth evolutions during gas pressure sintering of alumina. Isothermal sintering runs are performed under different nitrogen pressures: atmospheric pressure and 2 MPa. Experimental data are fitted thanks to constitutive laws in order to understand nitrogen pressure effect on densification and grain growth mechanisms of a fine-grained alumina. An optimal run of densification is proposed as an application of these results.     

Chromate leaching from inhibited primers: Part I. Characterisation of leaching

Leaching and characterisation studies have been undertaken on two chromate-inhibited epoxy polyamide primers. Leaching was carried out in 5% (w/v) NaCl solutions at different pH values (1, 3, 5 and 7) and the amount of Cr released into solution was monitored over time. Cr release was initially high, but as the immersion time increased the leaching from the primers slowed. Prior to and after immersion, the primers were characterised by a number of techniques including electron microprobe analysis, X-ray microdiffraction, Raman spectroscopy, and positron annihilation lifetime spectroscopy. The unexposed primers were found to contain the inorganic phases SrCrO₄, BaSO₄ and TiO₂ (anatase or rutile). Upon immersion, water uptake by the primers was observed, together with a decrease in the amount of SrCrO₄ in the primers. These studies provide insights into the mechanism of chromate leaching from inhibited primers.     

Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion: II. Application feasibility

Application feasibility of the accelerated deasphaltening process for simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion has been examined with a pilot plant having capacity of 1.590 m3/day. The solvent (n-pentane) was injected into the emulsion from three locations with progressively increasing temperature from 423 K. The first solvent injection precipitated the asphaltenes in bitumen, the second broke the emulsion and facilitated the phase separation, and the third extracted the oil that remained in heavy asphaltenes/water phase. The effects of operation parameters such as temperature, solvent/bitumen ratio, feed rate and feedstock composition on the quality of DAO (Deasphaltening oil) were investigated. The DAO with the yield of ~ 80 wt.% and asphaltene content of < 0.5 wt.% was produced under optimal operating conditions, and the residual product was a porous solids containing 38% sulfur, 47% nitrogen, 64% MCR, and 85% metals (nickel and vanadium) of the bitumen. For a real application in oil industry, other important aspects including energy efficiency, solvent recovery and water purification have been discussed.     

Non-destructive characterisation of alumina/aluminium titanate composites using a micromechanical model and ultrasonic determinations: Part II. Evaluation of microcracking

A method for non-destructive detection of microcracks in ceramic composites is described. The method involves the combination of ultrasound characterisation with the application of a three-phase micromechanical model, which considers cracks and pores as void constituents. Four alumina-aluminium titanate materials with different levels of microcracking, from no cracks (monophase alumina) to severely cracked (alumina + 40 vol.% of aluminium titanate) including an alumina + 10 vol.% aluminium titanate material with incipient microcracking have been developed to test the validity of the method. Specimens have been fabricated by colloidal processing and the longitudinal and transverse ultrasound velocities have been determined by the ultrasonic pulse-echo and transmission ultrasound-immersion techniques, employing a digital signal processing. It has been demonstrated that it is possible to differentiate between pores and microcracks, both modelled as void constituents, in terms of the aspect ratio.     

Simulation of the photopolymerization gradient inside a pigmented coating: Influence of TiO2 concentration on the gradient

The UV light behavior crossing a thick scattering and absorbing paint film has been modelled by a four-flux radiative transfer theory. For all that, the scattering characteristics of the coating as well as the calculation of the UV intensity decay through the coating thickness were measured versus TiO₂ pigment concentration. Thanks to these results, the conversion profiles in the coating thickness were obtained by numerical modeling and the influence of TiO₂ pigment concentration on these conversion profiles was discussed.     

Investigation of zinc chromatation: Part II. Electrochemical impedance techniques

A mechanism to explain the formation of a chromate layer on zinc is proposed. It assumes that a ZnO inner film blocks the zinc surface on which the chromate layer grows. This layer has gel-like properties. The diffusion of the protons across the chromate layer and across the solution is supposed to be the kinetically limiting steps. This model was derived and experimentally tested in terms of impedance. The influences of the immersion time, mass transport, and pH of the chromatation solution were examined. A rather good agreement was found between the predictions of the model and the experimental results.     

Pelletised fuel production from coal tailings and spent mushroom compost — Part I: Identification of pelletisation parameters

This study investigates the technology of manufacturing pellet blends for energy production from two discarded materials in industry. Coal tailings material is the fine discard produced as a result of coal cleaning. Although it still has a significantly high calorific value, over a million tonnes of coal tailings are deposited in lagoons every year in the UK alone. Spent mushroom compost (SMC) consists of fibrous compost substrate and a wet casing layer used during mushroom production. In the form of pellets, these materials become more homogeneous, easily stored and transported, and suitable for use in power plants or gasifiers. The characterisation of the fuel properties shows that the two materials have a complimentary status for pelletisation and energy production in terms of particle types, carbon source, calorific value and volatile matter content.     

Ash chemistry and mineralogy of an Indonesian coal during combustion: Part 1 Drop-tube observations

The paper reports a systematic and comprehensive laboratory investigation into the ash chemistry and mineralogical changes undergone by a low-rank Indonesian coal during combustion. Combustion experiments conducted in a drop-tube furnace included ash formation experiments (using cyclone and filter arrangement) under closely controlled conditions in the range of 1200–1400 °C and deposition experiments at a probe temperature of 750 °C. Tests conducted with raw coal, coal/additive mixtures and washed coal indicated significant changes in ash characteristics. Of the ash formation and deposit samples examined, the raw coal + bauxite showed the lowest glass content and high contents of corundum indicating low ash deposition propensities. When compared to the ash formation samples, the deposit samples showed even significantly lower glass contents and were enriched in quartz. With the exception of the raw coal + bauxite sample, all are characterized by high silica and iron and moderate aluminium contents. In contrast, the raw coal + bauxite sample have low silica and much higher alumina contents which is in agreement with XRD observations. QEMSCAN™ results showed that the ash particles are sparsely distributed suggesting lack of a deposit initiation layer. Experimental observations suggest that the use of raw coal with bauxite would appear to offer the best performance with respect to handling ash-related issues. Present findings are of practical significance to power utilities employing Indonesian coal as there is no comprehensive work reported in the literature on ash chemistry and mineralogy of such coals.     

Coal liquefaction by hydrogen produced from methanol: 3. Examination of reaction conditions

Coals were liquefied in a 50 ml autoclave using hydrogen produced from methanol with decomposition and hydrogenation catalysts under various conditions. The conversion increased with increasing reaction temperature and time. This reaction is more suitable for the liquefaction of lower-rank coals. The hydrogen pressure had little effect on the conversion in the range of the ratio of methanol to coal of 2 g/g. The use of a solvent is very effective in increasing the liquefaction, especially at short times.     

Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion: I. Fundamental development

Simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion by adding light paraffinic solvents was investigated with a bench-scale unit. Asphaltene precipitation in bitumen, emulsion breaking, and phase separation were found to be largely dependent on solvency and temperature. Increasing temperature facilitated the precipitation of asphaltenes in bitumen, and accelerated the separation of the light deasphalting oil (DAO)/solvent phase and the heavy asphaltenes/water phase. The removal of 98 +% asphaltenes and 99.9 +% water from the emulsion was achieved with the n-pentane/bitumen volumetric ratio of 3.0 in temperature range of 423–453 K. The interaction between asphaltene particles and water droplets is actually beneficial to the removal process. For process design and optimization, the operation pathway including two-step solvent injections at different temperature, the supercritical recovery of solvent from DAO stream and the solidification of asphaltenes by depressurization, as well as other important issues have been addressed.     

Compatibility and incompatibility in anticorrosive painting: The particular case of maintenance painting

Despite being one of the most widely used anticorrosive protection techniques, painting often leads to incompatibility problems. Maintenance painting is also a common technique in the anticorrosive protection of metallic structures and equipment in general. When the maintenance work to be performed foresees using an old (aged) coating as an integral part of the new paint system to be applied, it is of vital importance to ensure the compatibility of the different components. Otherwise, premature failure, (bleeding, lifting blistering, cracking, etc.) may occur in a short time period. Using a previously defined methodology, this paper studies the behaviour of a number of new paint systems applied on aged paint coatings containing different types of finishing paints. Through the performance of accelerated and non-accelerated ageing tests it has been possible to select the new paint systems that are most suitable for application on old (aged) paint systems, thus allowing a reduction in the risk of incompatibility between the two.     

Film formation from monodisperse acrylic lattices: Part 3: Drying and ageing of acrylic latex films

The influence of drying/ageing on the structure and properties of acrylic latex films was investigated using turbidity measurements in combination with gravimetry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and water vapour permeability. Ageing above the minimum film formation temperature (MFFT) leads to marked changes in a dried latex film, whereas, after ageing below the MFFT, changes are hardly found. Above the MFFT there is a continuous change in the film properties with time. This becomes obvious from the decreases in the regenerated interference minimum, water vapour permeability and corrugation height. The influence of ageing on the water absorption of the films is less straight forward. It was expected that films with a more compact structure would absorb less water. This is correct for short drying times only, from 0.5 to 3 h. Ageing of better-dried films, however, yields the opposite result: by increase of the ageing time from 3 to 150 h the water uptake increases. There are various reasons for this increase; they are discussed briefly.     

Characterization of mercury- and zinc-doped alkali-activated slag matrix: Part II. Zinc

The compressive strength, setting time, pore structure and hydration product of Zn-doped, alkali-activated slag (AAS) matrix have been investigated by examination of physical properties, micropore analysis, thermal analysis, FTIR, SEM and TCLP methods. The results show that the effects of Zn²⁺ on the AAS matrix depend on Zn²⁺ ion concentrations. At low Zn²⁺ ion concentrations, little negative influences on the compressive strength, setting time and distribution of pore structure were observed. Moreover, low concentrations of Zn²⁺ ion could be effectively immobilized in the AAS matrix. For 2% Zn-doped AAS matrix, the hydration of AAS paste was greatly retarded and leaching from this matrix was higher than TCLP zinc limit even at 28 days. Based on the analyses of hydration products, the chemical fixation mechanisms are considered responsible for the immobilization of Zn²⁺ ions in the AAS matrix.     

Water-entrained cement-based materials : II. Experimental observations

This paper concerns a new concept for the prevention of self-desiccation in hardening cement-based materials. The concept is based on using fine, superabsorbent polymer (hydrogel, SAP) particles as a concrete admixture. This permits a controlled formation of water-filled macropore inclusions—water entrainment—in the fresh concrete. Consequently, the pore structure is actively designed to control self-desiccation. In the paper, experimental observations in relation to this technique are described and discussed. The observations show that self-desiccation can be controlled by water entrainment. The paper forms the second part of a series. In the first part, the theoretical background was presented [Cem. Concr. Res. 31(4) (2001) 647].     

Pyrrole-based silane primer for corrosion protection of commercial Al alloys: Part I: Synthesis and spectroscopic characterization

Chromate-free, direct-to-metal treatment using a pyrrole-based silane (PySi) was developed for protection against corrosion of as-received commercial wrought Al alloys of the series 1xxx, 2xxx, 5xxx and 6xxx. The metal surface was modified following the simple procedure for silane deposition by immersion in PySi hydrolyzed solution and curing. The spectroscopic characterization indicates that crosslinked composite PPySi network, containing both polysiloxane and polypyrrole units due to co-polymerization of PySi molecules, is produced by self-assembling of PySi soluble macro-oligomers onto the metallic substrates upon adsorption, with three-dimensional crosslink during heat treatment. Highly ordered well-packed and adherent PPySi film of the order of microns is obtained by just one immersion step in PySi primer. Control coatings of polymethylsiloxane (PMeSi) and polypyrrole (Ppy), the latter synthesized electrochemically, were investigated in parallel.     

Water electrolysis under microgravity: Part II. Description of gas bubble evolution phenomena

Water electrolysis is carried out in both alkaline (25 and 2 wt.% KOH) and acidic (0.1N H₂SO₄) solutions for 8 s under a microgravity (μ-G) environment realized in a drop shaft. The effects of gravitational strength on gas bubble evolution behavior are analyzed in consideration of various factors (bubble movement, bubble assembly and single bubble). Under a μ-G environment, a collection of fine gas bubbles forms a froth layer in alkaline solutions, whereas bubbles frequently coalesce in acidic solution. Moreover, H₂ gas bubbles in alkaline jump from a cathode surface and O₂ bubbles often coalesce on an anode. In acidic solution both H₂ and O₂ bubbles frequently coalesce on electrode surfaces. Such gas bubble movements are reflected in the coalescence number and bubble residence time. A single bubble is characterized by the bubble size and the dynamic contact angle between a gas bubble and a Pt electrode, however, these factors are not essentially influenced by the gravitational strength.     

Alkali sorption by C-S-H and C-A-S-H gels: Part II. Role of alumina

In Part I, it was shown that alkali partition between C-S-H gel and an aqueous phase can be represented by a partition function, R_d, the numerical value of which, at constant temperature, is defined by the Ca/Si ratio. This R_d value is constant or nearly so over wide ranges of NaOH and KOH concentrations up to ∼0.3 M. In the present paper, Al has been introduced to form C-A-S-H gels, and the influence of Al on alkali sorption properties was determined: Approximately 6-7% replacement of Si by Al was used. Microprobe evidence is presented to show that the Al is actually in solid solution. Introduction of Al into C-S-H markedly increases R_d, indicating enhancement of alkali binding. The results underpin and quantify the beneficial effects of alkali binding arising from the introduction of aluminous supplementary cementing materials, such as fly ash, into cement pastes.     

Optimization of cathode catalyst layer for direct methanol fuel cells: Part II: Computational modeling and design

The cathode catalyst layer in direct methanol fuel cells (DMFCs) features a large thickness and mass transport loss due to higher Pt loading, and therefore must be carefully designed to increase the performance. In this work, the effects of Nafion loading, porosity distribution, and macro-pores on electrochemical characteristics of a DMFC cathode CL have been studied with a macro-homogeneous model, to theoretically interpret the related experimental results. Transport properties in the cathode catalyst layers are correlated to both the composition and microstructure. The optimized ionomer weight fraction (22%) is found to be much smaller than that in H₂ polymer electrolyte fuel cells, as a result of an optimum balance of proton transport and oxygen diffusion. Different porosity distributions in the cathode CLs are investigated and a stepwise distribution is found to give the best performance and oxygen concentration profile. Influence of pore defects in the CLs is discussed and the location of macro-pores is found to play a dual role in affecting both oxygen transport and proton conduction, hence the performance. The reaction zone is extended toward the membrane side and the proton conduction is facilitated when the macro-pores are near the gas diffusion layer.