Fabrication of a miniature twin-fuel-cell on silicon wafer

The fabrication and performance evaluation of a miniature twin-fuel-cell on silicon wafers are presented in this paper. The miniature twin-fuel-cell was fabricated in series using two membrane-electrode-assemblies sandwiched between two silicon substrates in which electric current, reactant, and product flow. The novel structure of the miniature twin-fuel-cell is that the electricity interconnect from the cathode of one cell to the anode of another cell is made on the same plane. The interconnect was fabricated by sputtering a layer of copper over a layer of gold on the top of the silicon wafer. Silicon dioxide was deposited on the silicon wafer adjacent to the copper layer to prevent short-circuiting between the twin cells. The feed holes and channels in the silicon wafers were prepared by anisotropic silicon etching from the back and front of the wafer with silicon dioxide acting as intrinsic etch-stop layer. Operating on dry H₂/O₂ at 25 °C and atmospheric pressure, the measured peak power density was 190.4 mW/cm² at 270 mA/cm² for the miniature twin-fuel-cell using a Nafion 112 membrane. Based on the polarization curves of the twin-fuel-cell and the two single cells, the interconnect resistance between the twin cells was calculated to be in the range from 0.0113 Ω (at 10 mA/cm²) to 0.0150 Ω (at 300 mA/cm²), which is relatively low.     

A new cyano-bridged Ca(II)–Fe(III) complex containing both molecular square and linear trimetallic species

A new cyano-bridged Ca(II)–Fe(III) complex, [Ca₂(phen)₄(H₂O)₆Fe(CN)₆][{Ca(phen)₂(H₂O)₂Fe(CN)₆}₂]·3(phen)·(phenH)·14H₂O·CH₃OH (where phen=1,10-phenanthroline) 1 has been synthesized and structurally characterized. It contains a cyano-bridged trimetallic cationic species [Ca₂(phen)₄(H₂O)₆Fe(CN)₆]⁺ 1a with a nearly linear Ca–Fe–Ca arrangement, and an anionic species [{Ca(phen)₂(H₂O)₂Fe(CN)₆}₂]²⁻ 1b which has a cyano-bridged tetrametallic Ca–Fe–Ca–Fe molecular square framework. In both the species, the Ca atoms are eight coordinated with distorted anti-squareprismatic geometry and the Fe atoms have six coordinated octahedral geometry. The charge is balanced by the protonation of one phen molecule in the lattice.     

Preparation of highly efficient and stable Fe,Zn,Al-pillared montmorillonite as heterogeneous catalyst for catalytic wet peroxide oxidation of Orange II

Fe,Zn,Al-pillared montmorillonite (Mt) were prepared by ion exchange reaction. Effect of the Fe/Zn molar ratio in Fe,Zn,Al-pillaring solution on the structural properties of Fe,Zn,Al-Mt was examined. Characterization studies were performed by N₂-adsorption/desorption, ICP, FTIR, DR UV–Vis spectroscopy and XRD. The interlayer space, specific surface and volume of micropores of pillared-Mt was 18.8 Å, 157 m² g^?1 and 0.114 cm³ g^?1 respectively. Besides, the catalytic performance of Fe,Zn,Al-Mt was analyzed through wet peroxide oxidation of Orange II under mild experimental condition. The results indicated that the catalytic performance of Fe,Zn,Al-Mt was affected by the Fe/Zn molar ratio as following pattern: the obtained pillared solids with lower Fe/Zn molar ratios exhibited better catalytic performance and less iron leaching during the reaction. Moreover, the introduction of zinc into Mt shortened the induction time of reaction and improved the catalytic behaviour. Throughout this work, the chemical oxygen demand removal of OII was 77.1 % after the solution treated by Fe,Zn,Al(3/7)-Mt (defined as the Fe/Zn molar ratio of 3/7 in the pillaring solution) catalyst at temperature of 60 °C and atmospheric pressure of 1 atm.     

Effect of Electrodeposition Parameters on the Microstructure and Corrosion Behavior of ‎DCPD Coatings on Biodegradable Mg–Ca–Zn Alloy

In this study, DCPD (Brushite, CaHPO₄.2H₂O) coatings were prepared on the surface of a Mg–Ca–Zn alloy using different current density (0.15–1.2 mA/cm²) and deposition time (5–90 min). The results revealed that DCPD with needle‐like morphology was observed for the current density between 0.15 and 0.4 mA/cm²?, whereas ?plate‐like morphology was obtained at current density above 0.8 mA/cm². The results showed that surface roughness increased with increasing current density. The lowest corrosion rate of 0.14 mm/year was obtained for the dense and uniform DCPD coating ?at 0.4 mA/cm², while further increase has deleterious effect on the corrosion resistance.     

Cationic substitution in tricalcium aluminate

Cubic and orthorhombic crystals of tricalcium aluminate doped with Na₂O, Fe₂O₃ and SiO₂ were prepared and examined using an electron probe microanalyzer. The cationic ratios based on six oxygen atoms were derived from the oxide compositions. These data, together with those in previous studies for clinker aluminates containing Mg²⁺ and K⁺, provided excellent correlations between Al+Fe and Si (Al+Fe=2.001−1.03Si) and Ca+Mg and Na+K+Si [Ca+Mg=3.006−0.51(Na+K+Si)]. The chemical variation that is constrained by these equations is well accounted for by the general formula (Na,K)_2x(Ca,Mg)_3−x−y[(Al,Fe)_1−ySi_y]₂O₆, where x is the amount of Ca substituted by Na and K (0≤x<0.158), and y is the amount of Al substituted by Si (0≤y<0.136). The crystal system changed from cubic to orthorhombic with increasing x value. The substitution of Si and Fe for Al extended the solid solution range of the orthorhombic phase to lower values of x, while its effect on the solid solution range of the cubic phase was reversed.     

The solubilities of Fe,Ni, V and Na salts in concentrated aqueous H2SO4 solutions at temperatures between 400 and 460 K

When residual fuel oil, which contains up to 4 wt% S, is burned in boiler plant, H₂SO₄ is formed which condenses as aqueous solutions (65–90 wt% H₂SO₄) on surfaces in the cool back-end. The oil contains traces of other elements, in particular Na, V, Fe and Ni, which also deposit on these surfaces as either sulphates (Na, Fe, Ni,) or oxides (V). When designing techniques to control acid deposition and the corrosion which it subsequently causes, account must be taken of the degree to which the acid properties can be modified by taking these compounds into solution. A series of measurements of the solubilities of relevant compounds in acid solutions within the appropriate ranges of concentration and temperature (400–460 K) have been made. Sodium sulphate has by far the highest solubility (55 wt% in a solution originally containing 85 wt% H₂SO₄ at 423 K). Of the other compounds considered, only V₂O₅ exhibits a solubility of more than 2 wt%; for example, at 463 K, in 75 wt% H₂SO₄, solutions containing up to 16 wt% V₂O₅ can be formed. Solutions with up to 23 wt% V₂O₅ can be stabilised by the presence in solution of small amounts (～0.5 wt%) of Fe³⁺ ions. The structure of these solutions is discussed.     

“Deactivation of copper electrode” in electrochemical reduction of CO2

Metallic Cu electrode can electrochemically reduce CO₂ to CH₄, C₂H₄ and alcohols with high yields as revealed by the present authors. Many workers reported that formation of CH₄ and C₂H₄ rapidly diminishes during electrolysis of CO₂ reduction. This paper shows that such deactivation of Cu electrode is reproduced with electrolyte solutions prepared from reagents used by these workers. Deactivated Cu electrodes recovered the electrocatalytic activity for CO₂ reduction by anodic polarization at −0.05 V versus she in agreement with the previous reports. Features of the deactivation depend greatly on the individual chemical reagents. Purification of the electrolyte solution by preelectrolysis with a Pt black electrode effectively prevents the deactivation of Cu electrode. Anode stripping voltammetry of Cu electrodes, which were deactivated during electrolysis of CO₂ reduction, showed anodic oxidation peaks at ca. −0.1 or −0.56 V versus she. The severer the deactivation of the Cu electrode was, the higher electric charge of the anodic peak was observed. It is presumed that some impurity heavy metal, originally contained in the electrolyte, is deposited on the Cu electrode during the CO₂ reduction, poisoning the electrocatalytic activity. On the basis of the potential of the anodic peaks, Fe²⁺ and Zn²⁺ are assumed to be the major contaminants, which cause the deactivation of the Cu electrode. Deliberate addition of Fe²⁺ or Zn²⁺ to the electrolyte solutions purified by preelectrolysis exactly reproduced the deactivation of a Cu electrode in CO₂ reduction. The amount of the deposited Fe or Zn on the electrode was below the monolayer coverage. Electrothermal atomic absorption spectrometry (etaas) showed that Fe originally contained in the electrolyte solution is effectively removed by the preelectrolysis of the solution. Mechanistic difference is discussed between Fe and Zn in the deterioration of the electrocatalytic property of Cu electrode in the CO₂ reduction. The concentration of the impurity substances originally contained in the chemical reagents as Fe or Zn is estimated to be far below the standard of the impurity levels guaranteed by the manufacturers. Presence of trimethylamine in the electrolyte solution also severely poisons a Cu electrode in the CO₂ reduction. It was concluded that the deactivation of Cu electrode in CO₂ reduction is not caused by adsorption of the products or the intermediates produced in CO₂ reduction.     

A simple method to control the diameter of carbon nanotubes and the effect of the diameter in field emission

We developed a simple method to control the diameter of carbon nanotubes (CNTs) and studied the effect of the diameter of CNTs in field emission. We fabricated Fe nanoparticle arrays of uniform size by filling Fe ion solution in the pores of the anodic aluminum oxide membrane bonded to a silicon wafer. Then we used them as catalysts to fabricate CNTs at a high temperature of 950 °C. The diameter of the nanoparticles could be controlled by changing the concentration of Fe ion solutions and consequently that of CNTs from 5 to 20 nm. Coating the Si wafers with gold greatly increased the field emission. The CNTs showed a good field emission property of a low turn-on field (1.8 V/μm), very high current density (94 mA/cm²) and long-term stability (5 h for 10% degradation of current density from 1 mA/cm²). Decreasing the diameter of the CNTs increased the field emission, while the field emission stability was almost unaffected by the diameter and length.     

Correlating chemical and water purity to the surface metal on silicon wafer during wet cleaning process

Trace metals in hydrogen peroxide and high-purity water, used in wet cleaning of wafers, is correlated to the metallic contamination of the wafer surface since metal contamination adversely impacts IC device yield. Hydrogen peroxide with different level of trace metals, ranging from 100 ppt level to 10 ppb level, is used in the experiment to determine the level of selected metal deposition on the silicon surface. Significant amounts of these trace metallic impurities can be removed by subsequent treatment of the silicon wafer by an acidified solution of water. Contamination of a wafer surface by sodium is also correlated to the level of sodium present in deionized water used in the final rinsing of the wafer. The threshold and mechanism for metal deposition for various metals on wafer surfaces are different. This information is useful in determining purity requirements for process chemicals and improving the wet cleaning process for the next generation of semiconductor devices.     

Electrodeposition of zinc–iron alloy from an alkaline bath in the presence of sorbitol

The chronopotentiometric technique was used to analyze the electrodeposition of Fe–Zn film on a Pt electrode. Three different Fe³⁺/Zn²⁺ molar ratios, Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.%, were used in a solution containing sorbitol as the Fe³⁺-complexing agent, with a total concentration of the two cations of 0.20 M. Coloration of Fe–Zn films were light gray, dull dark gray and bright graphite, depending on the Fe³⁺/Zn²⁺ ratios in the deposition bath. The highest stripping to deposition charge density ratio was 47.5%, at 15 mA cm⁻² in the Fe26.8 wt.%–Zn73.2 wt.% bath. Energy dispersive spectroscopy indicated that the codeposition type of Fe and Zn in the Fe26.8 wt.%–Zn73.2 wt.% and Fe46 wt.%–Zn54 wt.% baths was normal at all j_d tested, while in the Fe66.6 wt.%–Zn33.4 wt.% bath there was a transitional current density from normal to equilibrium codeposition at 50 mA cm⁻². Scanning electron microscopy showed that Fe–Zn films of high quality were obtained from the Fe66.6 wt.%–Zn33.4 wt.% and Fe26.8 wt.%–Zn73.2 wt.% baths, since the films were smooth. X-ray analysis of the Zn–Fe films obtained at 15, 25 and 50 mA cm⁻², in the Fe26.8 wt.%–Zn73.2 wt.%, Fe46 wt.%–Zn54 wt.% and Fe66.6 wt.%–Zn33.4 wt.% plating baths, suggested the occurrence, in general, of a mixture of Fe₁₁Zn₄₀, Fe₄Zn₉, βFe, αFe, Fe₂O₃, Zn and PtZn alloys in the deposit.     

A novel series of photocatalysts with an ion-exchangeable layered structure of niobate

Ion-exchangeable niobates, A(M _n–1Nb _n O_3n+1) (A = Na, K, Rb, Cs; M = La, Ca etc.), with a layered perovskite structure are found to show a unique photocatalytic activity, especially in those H⁺-exchanged forms, for H₂ evolution from aqueous alcohol solutions as well as O₂ evolution from an aqueous silver nitrate solution.     

Atomic emission spectroelectrochemistry applied to dealloying phenomena II. Selective dissolution of iron and chromium during active-passive cycles of an austenitic stainless steel

Atomic emission spectroelectrochemistry was used to investigate selective dissolution of a 304 austenitic stainless steel sample in 2 M H₂SO₄. The partial dissolution rates of Fe, Cr, Ni, Mn, Mo, and Cu were measured as function of time during a series of potentiostatic triggered activation/passivation cycles. When first exposed to sulfuric acid solution, the steel sample was in a passive state with a total steady state ionic dissolution rate expressed as an equivalent current density of 10 μA cm⁻². A transition into the active and passive state could be triggered by cathodic (−700 mV vs. Ag/AgCl) and anodic (+400 to +700 mV vs. Ag/AgCl) potentiostatic pulses respectively of variable time. Excess Cr dissolution was observed during the activation cycle as compared to Fe and a depletion of Cr dissolution was observed during the passivation cycle. These results are interpreted in terms of the dissolution of a Cr rich passive layer during activation and selective dissolution of Fe, Mn, Ni and other elements to form a Cr rich passive layer during passivation. Quantitative analysis of the excess Cr showed that the residual film contained approximately 0.38 μg Cr/cm². Fe does not appear to be incorporated into the film at this early stage of passive film growth. Residual films of metallic nickel and copper were formed on the surface during the active period that subsequently dissolved during passivation.     

Elimination of organic contaminants from silicon wafers using high concentration ozonated-water

Treatment using water dissolved highly ozone (ozonated-water) was investigated to eliminate organic contaminations from the surface of silicon wafer. In order to enhance a concentration of ozone in ozonated-water, impurity soluble in ultra pure water, especially CO₂, was found to be significant. It is presumed that such impurity plays the role of inhibitor to suppress decomposition of O₃. The ozonated-water dissolved ozone of 100 mg/l and above showed excellent properties to eliminate resist as typical model of organic contaminants. It was found that the elimination rate of resist depends not on coexistence of H₂O₂ but on temperature of ozonated-water.     

ZnFe anomalous electrodeposition:: stationaries and local pH measurements

The kinetics of ZnFe codeposition was investigated in acid solutions. The effects of solution composition and pH were analyzed. Inhibition of H⁺ reduction and Fe deposition occurs with increasing Zn⁺⁺ concentration in sulfate solution. An activation of Zn deposition is also observed. Increasing pH causes Zn deposition activation during ZnFe codeposition. The anomalous codeposition is also favored in chloride medium. When alloy deposition becomes the main process, the interfacial pH is governed by the individual metal deposition that controls the kinetic behavior. The interfacial pH increases during separate Fe deposition, meaning that it occurs with simultaneous consumption of H⁺. Individual Zn deposition brings about an H⁺ inhibition. A correlation between the codeposition behavior of ZnFe and ZnNi in sulfate and chloride solutions suggests that the prevailing cathodic reaction governs the interfacial pH. Anomalous codeposition process does not seem to be associated with a saturation of any thermodynamic species at the electrode surface. It can only be described by kinetic arguments.     

Fabrication and electroanalytical characterization of label-free DNA sensor based on direct electropolymerization of pyrrole on p-type porous silicon substrates

Label-free DNA sensors based on porous silicon (PS) substrate were fabricated and electrochemically characterized. p-type silicon wafer was electrochemically anodized in an ethanolic hydrofluoric (HF) solution to construct a PS layer on which polypyrrole (PPy) film was directly electropolymerized. To achieve direct electropolymerization of PPy on PS substrate without pre-deposition of any metallic thin-film underlayer, a low resistivity wafer (0.01–0.02 Ω cm) was used. The rough surface of the PS layer allowed for a strong adsorption of the PPy film. Intrinsic negative charge of the DNA backbone was exploited to electrostatically adsorb 26 base pairs of probe DNA (pDNA) into the PPy film by applying positive bias. The pDNA was designed to hybridize with the target DNA (tDNA) which is the insertion element (Iel) gene of Salmonella enterica serovar Enteritidis. Dependence of peak current (i _p ) around 0.2 V vs Ag/AgCl on tDNA concentration and incubation time were shown from the cyclic voltammograms of PS/PPy + pDNA + tDNA substrates in a 0.01 M potassium perchlorate solution. Plot of i _p vs incubation time showed a reduction in current density (J) by ca. 29 μA cm⁻² every hour. Sensitivity obtained from a plot of i _p vs tDNA concentration was −166.6 μA cm⁻² μM⁻¹. Scanning electron microscopy (SEM) image of the cross-section of a PS/PPy + pDNA + tDNA multilayered film showed successful direct electropolymerization of PPy for a nano-PS DNA biosensor.     

Basic characteristics of spinel type manganese mixed oxide/titanium composite anodes for electroorganic redox catalysis

Manganese mixed oxide composite layers of about 1 μm thickness on titanium sheet as substrate were fabricated by firing of the corresponding nitrates at a typical temperature of 400°C in air. The activity of these anodes was evaluated by cyclic voltammetry (10 mV/s) and the stability was determined by chronopotentiometry (2.5 mA/cm²) in 1M H₂SO₄. The oxidation of 2-propanol was examined as a simple electroorganic model reaction. The quality of a first category of mixed oxides with general composition MnMe₂O₄ decresed in the order Me = Co, Ni, Fe. In a second group with the general formula MeMn₂O₄ a decrease in the order Me = Co, Cu, Fe, Ni, Ti, Zn, Cd, Ca, Mg, (Zn, Ge), Li was observed. The corresponding candidates of the second group were superior to those of the first. The anode service life τ of the optimum spinel anode CoMn₂O₄/Ti is dependent on the current density, according to j^λ τ = const. (λ = 1.7). Thus high current densities are precluded. The mechanism has been discussed in terms of a heterogeneous redox catalysis: surface Mn(VII) states are formed in a slow electrochemical step. In a subsequent fast chemical oxidation of the organic molecule the original reduced state is regenerated. This also explains the comparatively good service life of these anodes.     

The development of kinetics model for CO2 absorption into tertiary amines containing carbonic anhydrase

CO₂ absorption into aqueous solutions of two tertiary alkanolamines, namely, MDEA and DMEA with and without carbonic anhydrase (CA) was investigated with the use of the stopped‐flow technique at temperatures in the range of 293–313 K, CA concentration varying from 0 to 100 g/m³ in aqueous MDEA solution with the amine concentration ranging from 0.1 to 0.5 kmol/m³, and CA concentration varying from 0 to 40 g/m³ in aqueous DMEA solution with the amine concentration ranging from 0.05 to 0.25 kmol/m³. The results show that the pseudofirst‐order reaction rate (k_{0, amine}; s^?1) is significantly enhanced in the presence of CA as compared with that without CA. The enhanced values of the kinetic constant in the presence of CA has been calculated and a new kinetics model for reaction of CO₂ absorption into aqueous tertiary alkanolamine solutions catalyzed by CA has been established and used to make comparisons of experimental and calculated pseudo first‐order reaction rate constant (k_{0, with CA}) in CO₂‐MDEA‐H₂O and CO₂‐DMEA‐H₂O solutions. The AADs were 15.21 and 15.17%, respectively. The effect of pKa on the CA activities has also been studied by comparison of CA activities in different tertiary amine solutions, namely, TEA, MDEA, DMEA, and DEEA. The pKa trend for amines were: DEEA > DMEA > MDEA > TEA. In contrast, the catalyst enhancement in amines was in the order: TEA> MDEA> DMEA> DEEA. Therefore, it can be seen that the catalyst enhancement in the amines decreased with their increasing pKa values. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Synthesis and characterization of a magnetic hybrid material consisting of iron oxide in a carboxymethyl cellulose matrix

A magnetic hybrid material (MHM), consisting of iron‐oxide nanoparticles (?4 nm) embedded in sodium carboxymethyl cellulose (Na‐CMC) matrix was synthesized. The MHM synthesis process was performed in two stages. First, a precursor hybrid material (Fe(II)‐CMC) was synthesized from two aqueous solutions: Na‐CMC solution and FeCl₂ solution. In the second stage, the precursor hybrid material was treated with H₂O₂ under alkaline conditions to obtain the MHM. The results obtained from X‐ray diffraction show that the crystalline structure of iron oxide into MHM corresponds to maghemite or magnetite phase. Conversely, the results obtained from Fourier transform infrared (FTIR) spectroscopy reveal that the polymeric matrix (Na‐CMC) preserves its chemical structure into the MHM. Furthermore, in FTIR spectra are identified two characteristic bands at 570 and 477 cm^?1 which can be associated to maghemite phase. Images obtained by high resolution transmission electron microscopy and bright field scanning transmission electron microscope show that iron‐oxide nanoparticles are embedded in the Na‐CMC. Magnetic properties were measured at room and low temperature using a quantum design MPMS SQUID‐VSM magnetometer. Diagrams of magnetization versus temperature show that iron‐oxide nanoparticles embedded in Na‐CMC have a superparamagnetic‐like behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the Silicon Nitride Coating of Quartz Crucible on Impurity Distribution in Ingot‐Cast Multicrystalline Silicon

Multicrystalline silicon ingots were fabricated via the directional solidification method in a vacuum induction furnace using silicon nitride (Si₃N₄) as quartz crucible coating. The effect of Si₃N₄ coating on the impurity content, transference, and distribution in Si ingots was investigated. The results can be summarized as follows: The impurities contained in Si ingots, including Fe, Ca, Mn, Cu, P, and B, were found to decrease at varying degrees when the inner surface of the quartz crucible was coated with Si₃N₄. A mixed layer composted by Si₃N₄ and Si was observed on the surface of the Si ingot. This mixed layer provided microdefects for the nucleation of metallic impurities. The Fe and N contents in the Si/Si₃N₄ mixed layer changed with the same tendency, and FeSi₂ particles formed on the Si/Si₃N₄ crystalline boundary. Both Fe and Ca precipitated in the SiC particles near the Si ingot/Si₃N₄‐coating interface.     

In situ oxygen atom erosion study of a polyhedral oligomeric silsesquioxane-polyurethane copolymer

The surface of a polyhedral oligomeric silsesquioxane-polyurethane copolymer has been characterized in situ using X-ray photoelectron spectroscopy before and after exposure to incremental fluences of oxygen atoms produced by a hyperthermal oxygen atom source. The data indicate that the atomic oxygen initially attacks the cyclopentyl groups that surround the polyhedral oligomeric silsesquioxane cage most likely resulting in the formation and desorption of CO and/or CO₂ and H₂O from the surface. The carbon concentration in the near-surface region is reduced from 72.5 at.% for the as-entered surface to 37.8 at.% following 63 h of O-atom exposure at a flux of 2.0 × 10¹³ O atom/cm²-s. The oxygen and silicon concentrations are increased with incremental exposures to the O-atom flux. The oxygen concentration increases from 18.5 at.% for the as-entered sample to 32.6 at.% following the 63-h exposure, and the silicon concentration increases from 8.1 to 11.1 at.% after 63 h. The data reveal the formation of a silica layer on the surface, which serves as a protective barrier preventing further degradation of the polymer underneath with increased exposure to the O-atom flux.