Characterization of a lacquer film formulated with phosphating reagents for corrosion protection of galvanized substrates

This paper analyzes the chemical composition of the interface resulting from the application of an organic coating (lacquer) containing phosphating reagents on galvanized steel, galvanneal, and galfan substrates and its stability after short periods of exposure to condensing humidity and UV light (UVCON test). X-ray photoelectron spectroscopy (XPS) has shown that the lacquer drying process gives rise to a number of discontinuities on the lacquer surface (pores) exposing the phosphate layer formed on the original metallic coating surface. It is interesting to note the detection of fluoride and nitrite ions and phosphoric acid not combined with zinc (perhaps as HPO₄ ²⁻ and H₂PO₄ ⁻) on the lacquered surfaces before testing, which suggests a tendency of these species to concentrate on the outer surface of the phosphate layer or at the lacquer-phosphate layer interface (in zones covered by the lacquer). After one day of exposure to the UVCON test, XPS reveals the disappearance of the fluoride and nitrite ions and of the free phosphoric acid. After 15 days of exposure to the UVCON test, the carbon content is seen to have decreased considerably, while the zinc, phosphorus, and titanium contents have risen. The low atomic percentages of carbon (only moderately higher than those obtained with the coatings in bare state) and Zn/P atomic ratios close to 1.5 suggest the removal of a very substantial percentage of the lacquer, leaving the zinc phosphate formed on the surface of the different metallic coatings exposed. This quick and significant drop in the lacquer content barely seems to have a repercussion on the degradation of the metallic substrate during the UVCON test, since its visual aspect remains unaltered.     

Photocatalytic decomposition of N2O on Cu+/Y-zeolite catalysts prepared by ion-exchange

Insitu characterization of Cu⁺/Y-zeolite catalysts and their photocatalytic reactivities for the decomposition of N₂O into N₂ and O₂ have been investigated by means ofin situ photoluminescence, XAFS, and ESR techniques along with an analysis of the reaction products. It was found that Cu(I) ions included within the nanopores of Y-zeolite exist as the [Cu(I)--Cu(I)] dimer species as well as the isolated Cu(I) monomer species, their ratio being much dependent on the SiO₂/Al₂O₃ ratio of Y-zeolite. UV irradiation of these Cu⁺/Y-zeolite catalysts in the presence of N₂O led to the photocatalytic decomposition of N₂O into N₂ and O₂ at temperatures as low as 275 K. The electronically excited state of Cu(I) ion (3d⁹4s¹ state) plays a vital role in the photocatalytic decomposition of N₂O into N₂ and O₂. The photocatalytic reactivity of these Cu⁺/zeolite catalysts was found to be strongly affected by the local structure of the Cu(I) ions which could easily be modified by changing the SiO₂/Al₂O₃ ratio of Y-zeolite. The isolated linear 2 coordinated Cu(I) monomer species formed on Y-zeolite having a moderate SiO₂/ A1₂O₃ ratio exhibited a high photocatalytic reactivity for the direct decomposition of N₂O into N₂ and O₂, clearly showing the importance of the coordinative unsaturation of the active sites.     

An efficient method for a numerical description of virgin olive oil color with only two absorbance measurements

Four polynomial expressions are obtained that provide a good approximation and an easy, rapid calculation of the chromatic coordinates and the chroma—L ^*, a ^*, b ^*, and C—for the illuminant C and the standard observer, for a virgin or extra virgin olive oil; absorbance is measured at only 480 and 670 nm. These are as follows: L ^*=0.556458(A₄₈₀)²−2.51145A₄₈₀+0.55504(A₆₇₀)²−8.53016A₆₇₀+98.4089; a ^*=0.177372(A₄₈₀)²+2.1363A₄₈₀+1.43254(A₆₇₀)²−0.789231A₆₇₀−13.9246; b ^*=−16.0277(A₄₈₀)²+79.8932A₄₈₀−5.06558(A₆₇₀)²+3.36169A₆₇₀+31.9405; C=−15.8439(A₄₈₀)²+78.9312A₄₈₀−5.26784(A₆₇₀)²+3.56917A₆₇₀+33.3927. These give acceptable results, making the method a practical alternative to the extremely laborious Commission Internationale d’Eclairage (CIE) L ^* a ^* b ^* system, by which 391 absorbance values must be measured individually, nanometer by nanometer, before applying more complex equations. The validity of the proposed method has been confirmed by comparison, using a set of 20 sample oils different from the set of 25 oils used to generate the order of the equations. The variations between the values provided by the proposed and standard methods, respectively, had a mean of 0.00 for each of the chromatic variables—L ^* , a ^* , b ^* , and C; SD were moderate (0.71, 0.52, 1.22, and 1.22, respectively); the root mean square and the R ²-terms also confirmed the validity of the method.     

Zosteric acid—An effective antifoulant for reducing fresh water bacterial attachment on coatings

Zosteric acid, a natural product present in eelgrass, has been found to prevent the attachment of some bacteria and barnacles. The results indicate that it may also be effective at reducing the early stages of biofouling, such as the attachment of bacteria that lead to a biofilm. In this study, the ability of zosteric acid in reducing the early stages of fouling was evaluated using attachment studies of fresh water bacteria via two approaches. First, plain coatings were submersed in water containing zosteric acid and either enriched Lake Erie bacteria or Pseudomonas putida, a model fresh water bacteria. It was found that zosteric acid with a concentration one-tenth of its EC₅₀ (the concentration eliminates 50% of the bacteria) was able to reduce bacterial attachment by more than 90%. The second approach incorporated zosteric acid into silicone coatings in the presence of a common solvent to achieve the slow release of zosteric acid; such coatings were then subjected to the bacterial attachment. A ～75% reduction in bacterial attachment was found for 1 wt% zosteric acid entrapped Sylgard^® 184, a model silicone coating, but the reduction only achieved ～55% for 1 wt% zosteric acid entrapped in a commercial silicone coating, RTV11.     

Gas absorption of carbon dioxide in a hollow fiber contained liquid membrane absorber

Experiments on the absorption of CO₂ into a hollow fiber contained liquid membrane absorber were performed. The feed gas was a mixture of CO₂ and N₂, absorbent liquid was 2-amino-2-methyl-l-propanol and the hollow fiber was a microporous hydrophobic polytetrafluoroethylene membrane. Outlet concentration of CO₂ from the absorber decreased as absorbent concentration increased, gas flow rate increased and were held constant for speed of agitation, but had a maximum value in the range of inlet concentration of CO₂ from 5 to 40 mole%. The reaction rate constant obtained for CO₂-amine system was 231 I/mol · s at 25 °C using a flat stirred vessel, and the membrane-side-mass-transfer coefficient was 1.217 × 10⁻⁵ mol/cm² · s · atm in CO2/N2-amine system. A diffusion model based on mass transfer with fast-reaction was proposed to predict the performance of the absorber.     

Thermal shock resistance and mechanical properties of La2Ce2O7 thermal barrier coatings with segmented structure

La₂Ce₂O₇ (LCO) is a promising candidate material for thermal barrier coatings (TBCs) application because of its higher temperature capability and better thermal insulation property relative to yttria stabilized zirconia (YSZ). In this work, La₂Ce₂O₇ TBC with segmentation crack structure was produced by atmospheric plasma spray (APS). The mechanical properties of the sprayed coatings at room temperature including microhardness, Young's modulus, fracture toughness and tensile strength were evaluated. The Young's modulus and microhardness of the segmented coating were measured to be about 25 and 5 GPa, relatively higher than those of the non-segmented coating, respectively. The fracture toughness of the LCO coating is in a range of 1.3–1.5 MPa m^1/2, about 40% lower than that of the YSZ coating. The segmented TBC had a lifetime of more than 700 cycles, improving the lifetime by nearly two times as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Improvement of the growth of Arthrospira (Spirulina) platensis from Toliara (Madagascar): Effect of agitation, salinity and CO2 addition

Arthrospira (Spirulina) platensis Toliara isolated from alkaline and salt lakes in the south-western area of Madagascar is a potential source of proteins that could efficiently fight against food deficiency in developing countries like Madagascar. Up to now, productivity in this country has been low, so a better understanding of the growth conditions of this species is needed to improve its production. Growth experiments were undertaken in bubble columns at laboratory scale. The influence of agitation of the culture, medium salinity (ranging from 13 to 35 g L⁻¹) and CO₂ addition (ranging from 0 to 2%, v/v) on growth and protein content was examined. Because Arthrospira cells are fragile, a bubble column without additional mixing gave the best growth. Arthrospira (Spirulina) platensis showed higher specific growth rate (μ_max) and protein content for lower salinity. Addition of 1% of CO₂ improved the productivity by near 60%. The feasability of semi-continuous culture was demonstrated and optimal culture conditions led to a mean productivity of 0.22 ± 0.03 g L⁻¹ d⁻¹, a mean specific growth rate of 0.015 ± 0.002 h⁻¹ and a protein content of 53 ± 2% of total dry weight.     

Electrochemical behaviour of thin films deposited by plasma DBD torch on copper: An O2-diffusion barrier

In the field of corrosion protection, the research of environmentally friendly coating processes is one of the research topics. The use of gaseous atmospheric plasma, especially dielectric barrier discharge (DBD) plasma is an interesting way to rapidly form a thin protective coating. The aim of this work is to characterize the electrochemical behaviour of a SiO_xC_yN_z film, formed from different organosilicon precursors, in neutral corrosive environment on copper. The film morphology and composition were determined by transmission electron microscopy (TEM) observations and X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour of the different treated copper was studied by stationary techniques and electrochemical impedance spectroscopy (EIS). With the same plasma parameter, the kind of organosilicon precursor determines the chemical stability of the coatings in water, then their protective properties. When the SiO₂-like structure contains a low carbon level, the SiO_xC_yN_z films present a good stability in water, and acts clearly as an O₂ barrier membrane.     

Co-decorated carbon nanotube-supported Co–Mo–K sulfide catalyst for higher alcohol synthesis

Using chemical reduction-deposition method, a type of metallic cobalt-decorated multi-walled carbon nanotubes, noted as y%(mass percentage)Co/MWCNTs, was prepared. TEM, SEM and XRD measurements demonstrated that the metallic cobalt was evenly coated on the MWCNT substrate, with granule-diameter of the Co _x ⁰ -crystallites of 5–8 nm. Using the y%Co/MWCNTs as support, a type of supported Co–Mo–K sulfide catalysts, noted as x%(Co _i Mo _j K _k )/(y%Co/MWCNTs), for higher alcohol synthesis (HAS) was developed. It was experimentally shown that using the Co-modified MWCNTs in place of simple MWCNTs or activated carbon (AC) as the catalyst support led to a significant increase in activity of CO hydrogenation conversion and improvement in the selective formation of C₂₊-alcohols. Under the reaction condition of 5.0 MPa, 613 K, CO/H₂/N₂ = 45/45/10 (v/v) and GHSV = 3600 ml_STPh⁻¹ g _−cat. ⁻¹ , the observed STY of C_1–4-alcohols reached 154.1 mgh⁻¹g _−cat. ⁻¹ at 12.6% conversion of CO over the 11.6%(Co₁Mo₁K_0.6)/(6.4%Co/MWCNTs) catalyst, which was 1.76 and 2.33 times as high as that (87.7 and 66.1 mgh⁻¹g _−cat. ⁻¹ ) of the reference systems supported by simple MWCNTs and AC respectively. Ethanol became the predominant product of the CO hydrogenation, with carbon-based selectivity ratio of C_2–4-alcohols to CH₃OH reaching 3.6 in the products. It was experimentally found that using the Co-modified MWCNTs in place of simple MWCNTs or AC as the catalyst support caused little change in the apparent activation energy for the conversion of CO, but led to a slight increase in the molar percentage of catalytically active Mo-species (Mo⁴⁺) in the total Mo-amount at the surface of the functioning catalyst. Based upon the results of TPD investigation, it could be inferred that, under the reaction condition of HAS, there existed a considerably larger amount of adsorbed H-species and CO-species on the functioning catalyst, thus in favour of increasing the rate of a series of surface hydrogenation reactions in HAS.     

Synthesis of Magnetite Nanoparticles with PDLLA Corona

The ring-opening polymerization (ROP) of D,L-lactide (DLLA) initiated by tin(II) 2-ethylhexanoate (Sn(Oct)₂) on the surface-initiated magnetite (Fe₃O₄) nanoparticles was performed at 130 °C. Effects of the polymer molar mass and concentration on the amount of polymer on the surface were investigated. The number average molecular weights, M _n , that we obtained by both nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) methods fit well within the accuracy of the applied methods, and range from 1,100 g · mol⁻¹ to 4,040 g · mol⁻¹. The surface functionalization density for up to 3,900 initiation sites per particle was obtained. The composition of various particles with poly(D,L-lactide) (PDLLA) corona is by means of thermogravimetric analysis (TGA), and indicates magnetite (Fe₃O₄) content between 17 wt.% and 59 wt.%. An erratum to this article can be found at     

Effects of NH3·H2O pretreatment on the fabrication of uniform titania nanocoating in an aqueous solution

An investigation is reported of the TiO₂ nanocoating on the ZnS-based phosphor via a sol-gel method in an aqueous solution using titanium diethanolamine complex as the precursor. The pretreatment of ZnS phosphors with NH₃·H₂O is important to the coating process. When NH₃·H₂O was added into the ZnS phosphor suspension, OH⁻ promoted the hydrolysis of Zn²⁺ on the surface of ZnS phosphors, which resulted in the formation of Zn-OH. Zn-OH reacted with the hydrolysis product of titanium diethanolamine complex, thus the titania coatings were obtained. The coating morphology was strongly dependant on the pH of the pretreated ZnS phosphor suspension and the weight ratio of ZnS to TiO₂.     

Catalyst’s Sulfur Displacement by Thiophene, as Monitored by Exchange of 35S Radiotracer

The isotopic exchange has been studied between catalyst radiosulfur and H₂S, formed in thiophene hydrodesulfurization (HDS) (named S-displace) on alumina supported molybdena, on CoMoO_x, PdMoO_x, PtMoO_x and on silica–alumina supported NiWO_x. S-displace was compared with radiosulfur exchange data between catalyst radiosulfur and gas phase H₂S (S^exc) determined previously. The extent of S^exc was higher than that of the S-displace for Mo, CoMo in and NiW, whereas the extent of S-displace from PdMoO and PtMoO was significantly higher, than that of S^exc. Thiophene HDS product distribution data are discussed in terms of increased C=C hydrogenation and C–C hydrogenolysis activity, explained by increasing H₂S production with longer circulation time of the thiophene/H₂ mixture, The C₁/C₃<1 ratios among C₄-hydrogenolysis products indicate some coke formation. The decrease of thiophene HDS activity is presumably a consequence of increasing site-blocking with the formation of more H₂S and coke with longer duration of thiophene treatment.     

UV-protective treatment for Vectran® fibers with hybrid coatings of TiO2/organic UV absorbers

The high performance of Vectran^® fiber makes its application as an envelope material for airship feasible. The ultraviolet (UV) resistance of this fiber, however, is poor, and UV irradiation in the stratospheric environment causes rapid fiber aging. To protect Vectran^® fibers from UV irradiation, we prepared TiO₂ nanosols via a sol–gel method and added benzotriazole UV-1130, triazine Tinuvin^® 477, and hindered amine Tinuvin^® 123 to them to form organic/inorganic hybrid coatings. Fiber specimens were subjected to accelerated aging using a xenon arc weatherometer. Mechanical measurements as well as surface morphology and chemical composition analyses were performed to evaluate the UV-protective performance of different coatings. Hybrid coatings performed better than TiO₂ coatings in protecting fibers from UV. Among the hybrid coatings obtained, UV-1130 especially reinforced the UV-protective ability of the TiO₂ coating because of its strong UV absorbance. Although the performances of Tinuvin^® 477 and Tinuvin^® 123 were below optimal when combined with TiO₂ alone, both hybrids exhibited excellent synergistic effects when used together with UV-1130 and improved the UV-protective ability of the resultant hybrid coatings.     

Improving the electrochemical performance of Ni-rich cathode materials using a fast ion conductor coating of Li2O–B2O3–LiBr

The high-Ni layered metal oxide, LiNi_0.8Co_0.1Mn_0.1O₂ (LNCM811), has received widespread attention in the energy field because of its high specific capacity, but its large-scale applications are hindered due to severe capacity fading. Herein, a uniform and thin Li₂O–B₂O₃–LiBr-glass (LBBrO-glass) coating was deposited on LNCM811 by a liquid-phase coating and thermal treatment method. The experimental results suggested that the LBBrO-glass coating acted as a protective layer that inhibited transition metal dissolution and side reactions, which helped improve the electrochemical properties of LNCM811. Remarkably, after 200 cycles, the 2 wt% coating (LBBrO@LNCM-2) delivered a superior capacity retention of 88.9%, while only 71.8% was obtained for the pristine material (LNCM811). The discharge capacity of LBBrO@LNCM-2 was 163.5 mAh g^?1 at 5C, while it was only 139 mAh g^?1 for the pristine material.     

A new corrosion protection coating with polyaniline-TiO2 composite for steel

Organic coating strategies for corrosion protection with inherently conducting polymers have become important because of restriction on the use of heavy metals and chromates in coatings due to their environmental problems. This work presents the synthesis of polyaniline-TiO₂ composites (PTC) and the corrosion protection behaviour of PTC containing coating on steel. PTC was prepared by chemical oxidation of aniline and TiO₂ by ammonium persulfate in phosphoric acid medium. The PTC was characterized by FTIR, XRD and SEM techniques. Suitable coating with PTC was formed on steel using acrylic resin. Using electrochemical impedance spectroscopy, the PTC containing coating's behaviour in 3% NaCl immersion test and salt spray test has been found out. Results indicate that the coating containing PTC is able to maintain the potential of steel in passive region due to its redox property. The resistance of the coating containing PTC was more than 10⁷ Ω cm² in 3% NaCl solution after 60 days and 10⁹ Ω cm² in the salt spray test of 35 days. But the resistance of the TiO₂ containing coating was found to be less than 10⁴ Ω cm² in both the cases. The high performance of PTC containing coating is attributed to the passivation of steel by polyaniline.     

Dynamic simulation of cyclic voltammogram on the electrochemical reduction of VO2+ ions

An electrochemical reduction of VO²⁺ ions in a formic acid electrolyte was analyzed by cyclic voltammetry. A new four step reaction mechanism, EECE, was proposed to derive the mass transfer equation, and then it was solved by numerical method, which enabled us to obtain theoretical cyclic voltammograms. Kinetic parameters such as diffusion coefficients, rate constants and transfer coefficients, describing the VO²⁺ ion reduction system, were estimated by fitting the theoretical curve with the experimental data. The parameters obtained were then evaluated on their extended applicability in various concentrations and scan rates. It was shown that the theoretical voltammograms obtained using the above parameters fitted well with the experimental curves for the scan rate variation from 2 to 20 V/sec, while the deviation increased in proportion to the VO²⁺ ion concentration.     

Studying the influence of nano-Al2O3 particles on the corrosion performance and hydrolytic degradation resistance of an epoxy/polyamide coating on AA-1050

The aim of this work was studying the effects of addition of Al₂O₃ nanoparticles on the anticorrosion performance of an epoxy/polyamide coating applied on the AA-1050 metal substrate. For this purpose, the epoxy nanocomposites were prepared using 1, 2.5 and 3.5 (w/w) pre-dispersed surface modified Al₂O₃ nanoparticles. Field-emission electron microscope (FE-SEM) and ultraviolet–visible (UV–Vis) techniques were utilized in order to evaluate the nanoparticles dispersion in the epoxy coating matrix. The anticorrosion performance of the nanocomposites was studied by electrochemical impedance spectroscopy (EIS) (in 3.5 wt% NaCl solution for 135 days immersion) and salt spray test for 1000 h. The coating resistance against hydrolytic degradation was also studied by optical microscope and Fourier-transform infrared spectroscopy (FTIR). Results obtained from FE-SEM micrographs and UV–visible spectra showed that the nanoparticles dispersed in the coating matrix uniformly with particle size less than 100 nm even at high loadings. Results revealed that nano-Al₂O₃ particles could significantly improve the corrosion resistance of the epoxy coating. Nanoparticles reduced water permeability of the coating and improved its resistance against hydrolytic degradation.     

Simulation of SiO2/S coating deposition in a pilot plant set-up for coking inhibition

The anti-coking SiO₂/S coating was prepared on the inner surface of HK40 alloy tube in a pilot plant set-up by atmospheric pressure chemical vapour deposition (APCVD). The coating deposition was simulated using the computational fluid dynamics code, Fluent. The reaction parameters of the surface reaction for SiO₂ formation were determined based on the comparison between the experimental and the calculated values. Further, the influences of the inlet flow rate and mass concentration of source materials on the coating deposition rate were investigated. The simulated results showed that an increase of inlet flow rate led to the decrease of mass conversion of gas intermediates. The coating deposition rate along the reactor tube increased by 1–5 times as the inlet flow rate increased from 10 to 80 g min⁻¹. The mass conversion rate of the gas intermediate, Si(OH)₄, changed little at different inlet mass concentrations of source materials when the inlet flow rate was 30 g min⁻¹, and it had an increase for sulphide intermediates. The coating deposition rate along the reactor tube increased by about 10 times with increasing the inlet mass concentration from 0.2% to 2%. In the conditions we studied, SiO₂/S coating deposition was surface reaction rate limited. When the inlet flow rate was 30–40 g min⁻¹ with the resource material concentration of 1–1.6%, the SiO₂/S coating was about 15 μm at the tube outlet with the silicon-containing intermediate conversion rate of above 30% and a good uniformity of S along the reactor. This work provides a theoretical basis for optimisation of operational parameters of the anti-coking SiO₂/S coating preparation in the pilot plant set-up.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.