Hysteresis minor loop analysis of plastically deformed low-carbon steel

This work investigates applicability of magnetic hysteresis method for non-destructive testing of plastically deformed low-carbon steel. Recently introduced Magnetic Adaptive Testing procedure was used for evaluation of hysteresis minor loop data-sets to find the most sensitive parameter/s for indication of the material degradation stage. Inductive measurements were carried out on two identically degraded series of samples: magnetically closed window-shaped specimens, equipped with the magnetizing and the induction coils, and magnetically open strips, measured by an attached magnetizing yoke. The aim was to compare the results between these sample series in order to determine applicability and limitations of the single-yoke measurement technique. As a result, new magnetic parameters with the best sensitivity–stability ratio in a wide deformation range were introduced and proposed for utilization. Good qualitative coincidence between the measurement results on the closed and the open sample series was obtained in all range of magnetization. Several quantitative distinctions were explained and analyzed in order to improve the single-yoke technique.     

Dioxygen activation at non-heme iron: insights from rapid kinetic studies

One of the common biochemical pathways of binding and activation of dioxygen involves non-heme iron centers. The enzyme cycles usually start with an iron(II) or diiron(II) state and traverse via several intermediates (detected or postulated) such as (di)iron(III)-superoxo, (di)iron(III)-(hydro)peroxo, iron(III)iron(IV)-oxo, and (di)iron(IV)-oxo species, some of which are responsible for substrate oxidation. In this Account, we present results of kinetic and mechanistic studies of dioxygen binding and activation reactions of model inorganic iron compounds. The number of iron centers, their coordination number, and the steric and electronic properties of the ligands were varied in several series of well-characterized complexes that provided reactive manifolds modeling the function of native non-heme iron enzymes. Time-resolved cryogenic stopped-flow spectrophotometry permitted the identification of kinetically competent intermediates in these systems. Inner-sphere mechanisms dominated the chemistry of dioxygen binding, intermediate transformations, and substrate oxidation as most of these processes were controlled by the rates of ligand substitution at the iron centers.     

Conditioning of Rh/α-Al2O3 catalysts for H2 production via CH4 partial oxidation at high space velocity

Experimental evidence and literature indications suggest that the process of methane partial oxidation over Rh catalysts is structure sensitive. Crystal phases and Rh cluster size are thus expected to affect the final catalytic performance. In this work, it is observed that outstanding performances are obtained when the as-prepared catalysts are conditioned through repeated runs at increasing temperature and O₂/CH₄ = 0.56. Catalysts slowly activate, that is CH₄ conversion and synthesis gas selectivity progressively grow with time on stream. On the basis of TPO and CH₄ decomposition measurements, this phenomenon is herein explained as the result of a surface reconstruction driven by the repeated exposition to the reaction at high temperature; it is thought that such reconstruction tends to eliminate defect sites and disfavors C-deposition reactions (extremely fast over steps and kinks). Conditioning with O₂-enriched feed streams makes conditioning faster, since the accumulation of surface C-species is suppressed; however, the catalyst is eventually less active than a catalyst conditioned with standard feed mixtures. As an alternative, accumulation of carbon can be suppressed and surface reconstruction proceeds faster if the catalyst is directly exposed to the reaction at high temperature for several hours.     

Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10?500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between T_g and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δ?_α(M_n), the fraction of associated hydroxy groups (f_bond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity f_bond(M_n) in a modified Fox-Flory approach, the measured T_g(M_n) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.     

Mechanical properties of wollastonite‐reinforced polypropylene composites modified with SEBS and SEBS‐g‐MA elastomers

Mechanical properties of isotactic polypropylene/wollastonite/styrene rubber block copolymers (iPP/wollastonite/SRBC) composites were studied as a function of elastomeric poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) triblock copolymer (SEBS) and SEBS grafted with maleic anhydride (SEBS‐g‐MA) content from 0 to 20 vol%. Microphase morphology was stronger influenced by SRBC elastomers than by different wollastonite types. Higher encapsulation ability of SEBS‐g‐MA than SEBS caused more expressive core‐shell morphology and consequently higher notched impact strength as well as yield parameters, but lower Young's modulus. Higher ductility of the composites with SEBS than with SEBS‐g‐MA has been primarily caused by better miscibility of the polypropylene chains with SEBS molecules. Surface properties of components and adhesion parameters also indicated that adhesion at SEBS‐g‐MA/wollastonite interface, which was stronger than the one at the SEBS/wollastonite interface, influenced higher encapsulation of wollastonite particles by SEBS‐g‐MA. POLYM. ENG. SCI., 47:1873–1880, 2007. © 2007 Society of Plastics Engineers     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

Fabrication of TiO2-Organic Hybrid Dot Arrays Using Nanosecond Laser Interference Lithography

Laser interference lithography is an established fabrication technique for periodic arrays such as photonic crystals (PCs). In this paper, we report the fabrication of a TiO₂-organic hybrid periodic array by nanosecond laser interference lithography. TiO₂-organic hybrid films were prepared from titanium tetra- n -butoxide and 2-(methacryloyloxy) ethyl acetoacetate (MEAcAc) by the sol–gel method. The films were irradiated by using 10 ns pulses of 355 nm diffracted light from a Nd:yttrium–aluminum–garnet laser. The complexes formed by the Ti alkoxide and the MEAcAc were decomposed by laser irradiation, and the irradiated parts remained as periodic dot arrays on the substrate after the development. The two-dimensional array of this TiO₂-organic hybrid material was calcined at 450°C and formed an anatase TiO₂ dot array. The refractive index measured was 2.00. These dots were crack free and adherent to the substrate.     

Silica Colloidal Membranes with Enantioselective Permeability

Robust mesoporous membranes composed of silica spheres were surface-modified with chiral selector moieties, including small molecules, macrocycles, and polymers. Diffusion rates of enantiomers of a chiral dye through the resulting asymmetrically modified colloidal membranes were measured and the corresponding permselectivities were calculated. The membranes showed enantioselectivities in the range of 1.2–1.8, which were not significantly affected by the structure of the surface-immobilized chiral electors. This selectivity is on par with most reported polymer-based solid membranes and bulk liquid membranes. The enantioselectivity results from the surface-facilitated mechanism of transport of enantiomers through the mesopores.     

The effect of radiopacifiers agents on pH,calcium release,radiopacity, and antimicrobial properties of different calcium hydroxide dressings

The aim of this study was to evaluate the antimicrobial activity, pH level, calcium ion release, and radiopacity of calcium hydroxide pastes associated with three radiopacifying agents (iodoform, zinc oxide, and barium sulfate). For the pH and calcium release tests, 45 acrylic teeth were utilized and immersed in ultrapure water. After 24 h, 72 h, and 7 days the solution was analyzed by using a pH meter and an atomic absorption spectrophotometer. Polyethylene tubes filled with the pastes were used to perform the radiopacity test. For the antimicrobial test, 25 dentin specimens were infected intraorally in order to induce the biofilm colonization and treated with the pastes for 7 days. The Live/Dead technique and a confocal microscope were used to obtain the ratio of live cells. Parametric and nonparametric statistical tests were performed to show differences among the groups (P < 0.05). The pH analysis at 7 days showed significant differences (P < 0.05) among the groups. No differences among the pastes were found in the calcium release test on the 7th day (P > 0.05). The calcium hydroxide/iodoform samples had the highest radiopacity and antimicrobial activity against the biofilm‐infected dentin in comparison to the other pastes (P < 0.05). Calcium hydroxide mixed with 17% iodoform and 35% propylene glycol into a paste had the highest pH, calcium ion release, radiopacity, and the greatest antimicrobial action versus similar samples mixed with BaSO4 or ZnO. Microsc. Res. Tech. 78:620–625, 2015. © 2015 Wiley Periodicals, Inc.     

Design methodology for fully dynamic-controlled polynomial profiles and reduced tracking error in CNC machines

High speed and high precision on computer numerically controlled (CNC) machines are major issues for most industrial automation processes. Among the most important factors for precise motion control are the control law, the controller implementation, and the profile reference. The effects of the control law and controller implementation on the tracking error in CNC machines have been widely studied, while the issue of profile reference has not received the required attention. To improve the dynamics provided by the conventional profile reference, several techniques have been proposed, focusing on peak jerk limitation. The novelty of this work is to develop a generalized methodology designed for producing dynamically constrained higher degree piecewise polynomial profiles, without limits in maximum polynomial degrees. They lead to define in an arbitrary way the dynamics shape, while the peak dynamics values constrained are maintained in order to improve the tracking error on CNC systems and giving the possibility to design fully dynamic-controlled trajectories. For experimentation purposes, a two-axis proportional–integral–derivative controller and profile reference generator are implemented in a low-cost field programmable gate array. The experimentation demonstrates the efficiency of the proposed methodology, showing the peak jerk and tracking error reduction, compared against recent reports from literature.