Infrared reflection absorption study of carbon monoxide adsorption on Pd/Cu(1 1 1)

Pd-Cu bimetallic surfaces formed through a vacuum-deposition of Pd on Cu(1 1 1) have been discussed on the basis of carbon monoxide (CO) adsorption: CO is used as a surface probe and infrared reflection absorption (IRRAS) spectra are recorded for the CO-adsorbed surfaces. Low energy electron diffraction (LEED) patterns for the bimetallic surfaces reveal six-fold symmetry even after the deposition of 0.6 nm. The lattice spacings estimated by the separations of reflection high-energy electron diffraction (RHEED) streaks increase with increasing Pd thickness. Room-temperature CO exposures to the bimetallic surfaces formed by the Pd depositions less than 0.3 nm thickness generate the IRRAS bands due to the three-fold-hollow-, bridge- and linear-bonded CO to Pd atoms. In particular, on the 0.1 nm-thick Pd surface, the linear-bonded CO band becomes apparent at an earlier stage of the exposure. In contrast, the bridge-bonded CO band dominates the IRRAS spectra for CO adsorption on the 0.6 nm-thick Pd surface, at which the lattice spacing corresponds to that of Pd(1 1 1). A 90 K-CO exposure to the 0.1 nm-thick Pd surface leads to the IRRAS bands caused not only by CO-Pd but also by CO-Cu, while the Cu-related band is almost absent from the spectra for the 0.3 nm-thick Pd surface. The results clearly reveal that local atomic structures of the outermost bimetallic surface can be discussed by the IRRAS spectra for the probe molecule.     

Study of the order–disorder transition and martensitic transformation in a Cu–Al–Be alloy by EELS

Changes in 3d states occupancy associated with order–disorder transition and martensitic transformation in a Cu–Al–Be alloy was investigated by electron energy loss spectroscopy (EELS) in both high energy and low energy loss regions. From the high energy loss region, the Cu L_2,3 white-line intensities, which reflect the unoccupied density of states in 3d bands, was measured for three states of the alloy: disordered austenite, ordered austenite and martensite. It was found that the white-line intensity remains the same during order–disorder transition but appears slightly smaller in martensite, indicating that some electrons left Cu 3d bands or some hybridization took place during phase transformation. From the low energy loss region, the optical joint density of states (OJDS) was obtained by Kramers–Kronig analysis. As maxima observed in the OJDS spectra are assigned to interband transitions, these spectra can be used to probe changes in the electronic band structure. The analysis shows that during the martensitic transformation, the peaks positions and relative intensities in the OJDS spectra undergoes noticeable changes, which are associated with interband transitions.     

Quantitative analysis of multi-element oxide thin films by angle-resolved XPS: Application to ultra-thin oxide films on MgAl substrates

An original procedure has been developed for the quantitative analysis and microstructural interpretation of angle-resolved X-ray photoelectron spectra (AR-XPS) of very thin (<6 nm), multi-element oxide films as grown on metallic binary alloy substrates by, e.g., thermal or plasma oxidation. To this end, first an approach has been given to retrieve the different metallic, oxidic and oxygen primary zero-loss (PZL) intensities from the measured AR-XPS spectra of the bare and oxidized alloy. The principal equations for the determination of the oxide-film thickness, composition and constitution from the resolved PZL intensities have been presented. On this basis, various corresponding calculation routes have been distinguished. The procedure has been applied to the case of very thin (<6 nm), mixed (Mg, Al)-oxide films on bare Mg-based MgAl substrates as grown by dry, thermal oxidation at room temperature. The results obtained on the thickness, composition, defect structure and constitution of the oxide-film have been discussed as function of the bulk Al alloying content and the applied partial pressure of oxygen.     

Magnetization reversal of micropattern Fe bar array: Combination of vector and Bragg magneto-optical Kerr effect measurements

We report on a magneto-optical Kerr effect (MOKE) investigation of alternating wide and narrow Fe bars, forming a two-dimensional periodic array. The magnetization reversal was studied by regular longitudinal Vector-MOKE in specular geometry as well as in Bragg-MOKE geometry, using the diffraction spots from the grating for hysteresis measurements. With Vector-MOKE a two-step switching process for the wide and narrow Fe bars is observed, indicative for a narrow switching field distribution in this array. In addition, hysteresis loops were determined as a function of the diffraction order for the hard and easy axis direction. The loops at different orders of diffraction can qualitatively and quantitatively be described by Fourier transformations of micromagnetic simulations.     

Differential AC-chip calorimeter for glass transition measurements in ultrathin films

A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006     

Thermal stability of shear-induced precursor structures in isotactic polypropylene by rheo-X-ray techniques with couette flow geometry

Combined in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) studies using couette flow geometry were carried out to probe thermal stabilty of shear-induced oriented precursor structure in isotactic polypropylene (iPP) at around its normal melting point (162 °C). Although SAXS results corroborated the emerging consensus about the formation of “long-living” metastable mesomorphic precursor structures in sheared iPP melts, these are the first quantitative measures of the limiting temperature at which no oriented structures survive. At the applied shear, rate = 60 s⁻¹ and duration t_s = 5 s, the oriented iPP structures survived a temperature of 185 °C for 1 h after shear, while no stable structures were detected at and above 195 °C. Following Keller's concepts of chain orientation in flow, it is proposed that the chains with highly oriented high molecular weight fraction are primarily responsible for their stability at high temperatures. Furthermore, the effects of flow condition, specifically the shear temperature, on the distributions of oriented and unoriented crystals were determined from rheo-WAXD results. As expected, at a constant flow intensity (i.e., rate = 30 s⁻¹ and duration, t_s = 5 s), the oriented crystal fraction decreased with the increase in temperature above 155 °C, below which the oriented fraction decreased with the decrease in temperature. As a result, a crystallinty “phase” diagram, i.e., temperature versus crystal fraction ratio, exhibited a peculiar “hourglass” shape, similar to that found in many two-phase polymer–polymer blends. This can be explained by the competition between the oriented and unoriented crystals in the available crystallizable species. Below the shear temperature (155 °C), the unoriented crystals crystallized so rapidly that they overwhelmed the crystallization of the oriented crystals, thus depleting a major portion of the crystallizable species and increasing their contribution in the final total crystalline phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3553–3570, 2006     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

Charge density effects in salt‐free polyelectrolyte solution rheology

Solution rheology of 2‐vinyl pyridine and N‐methyl‐2‐vinyl pyridinium chloride random copolymers in ethylene glycol was studied over wide ranges of concentration and effective charge. The fraction of quaternized monomers α and the fraction of monomers bearing an effective charge f of these copolymers were measured using counterion titration and dielectric spectroscopy, respectively. Ethylene glycol is a good solvent for neutral poly(2‐vinyl pyridine), with very few ionic impurities. The viscosity η and relaxation time τ of dilute and semidilute unentangled solutions exhibit the scaling with concentration and effective charge expected by the Dobrynin model. Reduced viscosity data are independent of concentration in dilute solution, giving an intrinsic viscosity that depends on effective charge, and the experimental data obey the Fuoss law in the semidilute unentangled regime. Scaling concentration with the overlap concentration (c/c*) reduces these data to common curves, and c* ～ f ^?12/7 as predicted by the Dobrynin model, where f is the fraction of monomers bearing an effective charge. While the overlap concentration depends strongly on effective charge until counterion condensation occurs, the entanglement concentration c_e is surprisingly insensitive to effective charge, indicating that entanglement effects are not understood using the Dobrynin model. The terminal modulus G = η/τ depends only on the number density of chains G = ckT/N for c* < c < c_e, and G ～ c^3/2 for c > c_e independent of the effective charge. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2001–2013, 2006     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006