Enhanced Four-Electron Selective Oxygen Reduction Reaction at Carbon-Nanotube-Supported Sulfonic-Acid-Functionalized Copper Phthalocyanine

In the present work, the oxygen reduction reaction (ORR) is explored in an acidic medium with two different catalytic supports (multi-walled carbon nanotubes (MWCNTs) and nitrogen-doped multi-walled carbon nanotubes (NMWCNTs)) and two different catalysts (copper phthalocyanine (CuPc) and sulfonic acid functionalized CuPc (CuPc-SO₃⁻)). The composite, NMWCNTs-CuPc-SO₃⁻ exhibits high ORR activity (assessed based on the onset potential (0.57 V vs. reversible hydrogen electrode) and Tafel slope) in comparison to the other composites. Rotating ring disc electrode (RRDE) studies demonstrate a highly selective four-electron ORR (less than 2.5 % H₂O₂ formation) at the NMWCNTs-CuPc-SO₃⁻. The synergistic effect of the catalyst support (NMWCNTs) and sulfonic acid functionalization of the catalyst (in CuPc-SO₃⁻) increase the efficiency and selectivity of the ORR at the NMWCNTs-CuPc-SO₃⁻. The catalyst activity of NMWCNTs-CuPc-SO₃⁻ has been compared with many reported materials and found to be better than several catalysts. NMWCNTs-CuPc-SO₃⁻ shows high tolerance for methanol and very small deviation in the onset potential (10 mV) between the linear sweep voltammetry responses recorded before and after 3000 cyclic voltammetry cycles, demonstrating exceptional durability. The high durability is attributed to the stabilization of CuPc-SO₃⁻ by the additional coordination with nitrogen (Cu-N_x) present on the surface of NMWCNTs.     

Comparative holographic interferometry: A nondestructive inspection system for detection of flaws

Comparative holographic interferometry addresses a key problem of nondestructive evaluation: comparison of the resistance to strength in real time of two nominally identical specimens. After outlining the basis of comparative holography in flaw detection, the present paper reports on some new and complementary developments in comparative holographic interferometry. The proposed systems stand out by their ability to store the master displacement field in the interferometric setup. The integration of the storage capacity in the instrument considerably augments its potential in nondestructive routine inspection tasks. The visual display of the fringes contouring the difference in mechanical response is shown to improve considerably with the addition of auxiliary phase difference satisfying certain conditions. Methods for the generation of corresponding fringes are considered and their localization investigated in brief. Particular attention is devoted to the formation of the holographic moiré fringes. The influence of system misalignment on the moiré fringe interpretation is examined. A potential application of comparative holography to the quantitative evaluation of fatigue is described. Experimental evidence supporting the operational feasibility of the technique along with the results obtained in application to flaw detection are finally presented.     

Effect of a cocatalyst modifier in the synthesis of ultrahigh molecular weight polyethylene having reduced number of entanglements

The use of a hindered phenol to trap free trimethylaluminum (TMA) in methylaluminoxane (MAO) solutions has been reported to improve the performance of single‐site, homogeneous catalysts for olefin polymerization. In the present study, with the help of rheological analyses, we have investigated and compared the molecular weight, molecular weight distribution and entanglement density of ultrahigh molecular weight polyethylene synthesized with a single‐site catalyst activated by MAO and phenol‐modified MAO. While the number average molecular weight (M_n) of the obtained polymers remains the same for both activations, a higher yield and a higher entanglement density are found in the initial stages of polymerization on using phenol‐modified MAO as the cocatalyst. These results suggest that on using the phenol‐modified MAO as activator, a higher number of active sites are obtained. Surprisingly in the presence of untreated MAO, a tail in the higher molecular mass region is produced. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Estimation of Phase and Its Higher Order Derivatives from a Single Complex Interferogram

This paper reports a method for the simultaneous estimation of unwrapped phase and higher order phase derivatives from a single phase fringe pattern recorded in an optical interferometric setup, thereby overcoming substantial barriers to achieving such measurements. The proposed method considers the interference phase as a weighted linear combination of Gaussian radial basis functions defined along a given row or column at a time. The Gaussian radial basis functions are defined with a constant standard deviation and equally spaced centers. Unscented Kalman filter is employed for the accurate estimation of the weights of the basis functions using the state space representation of the spatial evolution of the interferogram. The estimated weights along with the numerically computed gradients of the basis functions also provide the estimations of phase derivatives of arbitrary order. The proposed representation of interference phase along with the unscented Kalman filter provides high robustness against the speckle noise. Simulation study is preformed to evaluate the dependence of the phase and phase derivative estimation accuracy on the selection of basis dimension and the noise level. Experimental results demonstrate the practical applicability of the proposed method.     

Normal vibrations and their dispersion in syndiotactic polystyrene

Normal modes and their dispersion are obtained for syndiotactic polystyrene (sPS) in the planar zigzag and s(2/1)2 helical conformations. Comparison is made with the spectra of isotactic polystyrene (ips) to identify the conformation-sensitive modes; for example, the 1221 cm^?1 mode is identified as a skeletal mode sensitive to chain structure and it also shows maximum dispersion. Bunching of dispersion curves and their intersection are among the characteristic features which are discussed. A check on the dispersion curves below 400 cm^?1 is made from the spectra of polystyrene oligomers.     

Sample Treatment Approaches for Trace Level Determination of Cesium in Hepatitis B Vaccine by Suppressed Ion Chromatography

The hepatitis B surface antigen manufactured by recombinant DNA technology is extracted from the culture media by density gradient centrifugation using cesium salts. Cesium is considered to be toxic, because it affects active ion transport by blocking potassium channels. The residual trace levels of cesium in hepatitis B vaccine samples are determined by suppressed ion chromatography. Hepatitis B vaccines contain various buffer salts, aluminum-containing adjuvants, proteins and traces of iron. The polyvalent cations (Al³⁺, Fe³⁺) and proteins degrade the chromatographic performance in terms of decreased retention time and poor reproducibility. Different sample preparation approaches were evaluated with the aim of eliminating these foulants: (1) filtration, (2) digestion and (3) digestion-protein precipitation. Quantitative elimination of these foulants was achieved in the digestion-protein precipitation sample clean-up approach. Cesium was separated on the IonPac CS17 column with suppressed conductivity detection. The results of the ion chromatography (IC) method were compared with ICP-MS analysis. The precision of determination was better than 6.5% (relative standard deviation) with a method detection limit of 45 ng mL⁻¹. The expanded uncertainty in the measurement at 95% confidence level (coverage factor 2) is better than 16.3%.

     

A Hemi‐metallocene Chromium Catalyst with Trimethylaluminum‐Free Methylaluminoxane for the Synthesis of Disentangled Ultra‐High Molecular Weight Polyethylene

Recently, it has been shown that by using a single‐site catalytic system having titanium as a metallic center, it is possible to tailor the entanglement density in the amorphous region of a semi‐crystalline ultra‐high molecular weight polyethylene (UHMWPE). This route provides the possibility to make high‐modulus, high‐strength uniaxially and biaxially drawn tapes and films, without using any solvent during processing. In this publication, it is shown that a single‐site catalyst having chromium as metallic center, proposed by Enders and co‐workers, can also be tuned to provide control on the entanglement density during synthesis of the UHMWPE. However, to achieve the goal some modifications during the synthesis are required. The synthesized polymers can be processed in the solid state below the equilibrium melting temperature, resulting in uniaxially drawn tapes having tensile strength and modulus greater than 3.5 N/tex and 200 N/tex, respectively. Rheological studies have been performed to follow the increase in entanglement density in melt state with time.

     

Magnetic properties of stuffed copper chromium tellurides Cu1+xCr2+yTe4 (x=0-1, y<0.3)

We present a detail study of the effect of excess metal atoms on the magnetic properties of Cu_1+xCr_2+yTe₄ at 2-400 K. With the increase in x=0-1 and y<0.3, these compounds retain metallic behavior, while ferromagnetic ordering temperature reduces from 325 to 160 K. Our low field susceptibility χ_ac measurements reveal a second transition on cooling below the ferromagnetic ordering; the transition at around 160-180 K intensifies with the excess amount of copper and chromium atoms. The value of spontaneous magnetization at 2 K remains between 2.6 and 2.9μ_B across all the compositions and it reduces with temperature as M(T)∼A₀T^3/2+A₁T^5/2, as expected for the excitation of Bloch's spin waves in a model of the Heisenberg ferromagnet. Our terminal composition Cu_1.9Cr_2.25Te₄ showed only second transition at 160 K with short range magnetic order much above the transition temperature and in the absence of the specific heat jump at this temperature. The magnetic properties are explained as a result of random magnetic anisotropy in the excess-metal compositions induced by the interstitial atomic defects in their parent spinel structure. The large stuffing of cations has been made possible in the telluride compounds because of the large size of tellurium and also by the covalent bonding that stabilizes the defect structure.