Surface morphology of cellulose films prepared by spin coating on silicon oxide substrates pretreated with cationic polyelectrolyte

Flat cellulose films were prepared and morphologically modified by spin coating a cellulose/N-methylmorpholine-N-oxide/H₂O solution onto silicon oxide substrates pre-coated with a cationic polyelectrolyte. Spin-coated cellulose films were allowed to stably form on the silicon oxide substrates by pretreatment with either polydiallyldimethylammonium chloride (PDADMAC) or polyvinylamine (PVAm). The film surfaces obtained were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). AFM topographical images of the cellulose film surfaces showed a different morphology depending on the underlying polymer, where PVAm pretreatment brought about an anisotropic surface topology. These results suggest that the specific attraction acting at the cellulose/polymer interface influences both the film formation and surface morphology of the cellulose layer. Differences in the solvent used to precipitate cellulose caused variations in the surface roughness by affecting the cellulose separation behavior. The morphological features of spin-coated cellulose film surfaces could be altered to some extent by these film preparation techniques.     

Design of weakly-coupled three-spatial-mode rectangular-ring core fiber for short-reach MDM networks in C + L band

We propose a novel weakly-coupled three-spatial-mode rectangular-ring core fiber for short-reach mode-division multiplexing (MDM) networks in C?+?L band. We investigate the influence of geometrical parameters on n_eff, min?n_eff, and A_eff with regions that meet the three-spatial-mode condition of the proposed fiber. Bending loss of each guided mode and DMD between adjacent spatial modes are also studied. Large effective refractive index difference between adjacent spatial modes is achieved with min?n_eff?~?0.004. Results imply that the designed fiber can simplify or eliminate MIMO-DSP for short-reach MDM networks such as optical interconnects, data centers, and optical access networks.     

Studies on terbium activated yttrium based tantalate phosphors

Terbium activated yttrium niobium tantalate phosphors were prepared by solid-state reaction and were characterized by photoluminescence measurements, X-ray diffraction and scanning electron microscopy. Photoluminescence (PL) of Y_0.95Tb_0.05Ta_1?xNb_xO₄ phosphors (x = 0–1) are influenced by the host-lattice composition, degree of crystalline order and particle morphology and size. The effect of the morpho-structural properties on PL characteristics of Y(Ta,Nb)O₄:Tb powders is reported.     

Properties of Cellulose Regenerated from Powerful 1-Butyl-3-methylimidazolium Acetate/Dimethyl Sulfoxide Solvent

1-butyl-3-methylimidazolium?acetate C₄mim][CH₃COO]/dimethyl sulfoxide/DMSO can effectively dissolve cellulose at ambient temperature without any heating. However, the thermostability, morphology, and structure of cellulose regenerated from the [C₄mim][CH₃COO]/DMSO solvent is little known. Therefore, in this work, the regenerated cellulose was prepared and characterized by scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and the degree of polymerization (DP) measurements. The results indicated that the regenerated cellulose film displayed homogeneous structures; no chemical reaction occurred between cellulose and [C₄mim][CH₃COO] as well as DMSO during the dissolution and precipitation processes. The regenerated cellulose had good thermal stability, similar to the original cellulose, and the macromolecular chains of cellulose were hardly broken during the dissolution and precipitation processes.     

Cavitation milling of natural cellulose to nanofibrils

Cavitation holds the promise of a new and exciting approach to fabricate both top down and bottom up nanostructures. Cavitation bubbles are created when a liquid boils under less than atmospheric pressure. The collapse process occurs supersonically and generates a host of physical and chemical effects. We have made an attempt to fabricate natural cellulose material using hydrodynamic as well as acoustic cavitation. The cellulose material having initial size of 63 micron was used for the experiments. 1% (w/v) slurry of cellulose sample was circulated through the hydrodynamic cavitation device or devices (orifice) for 6 h. The average velocity of the fluid through the device was 10.81 m/s while average pressure applied was 7.8 kg/cm². Cavitation number was found to be 2.61. The average particle size obtained after treatment was 1.36 micron. This hydrodynamically processed sample was sonicated for 1 h 50 min. The average size of ultrasonically processed particles was found to be 301 nm. Further, the cellulose particles were characterized with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) to see the effect of cavitation on crystallinity (X_c) as well as on melting temperature (T_m). Cellulose structures consist of amorphous as well as crystalline regions. The initial raw sample was 86.56% crystalline but due to the effect of cavitation, the crystallinity reduced to 37.76%. Also the melting temperature (T_m) was found to be reduced from 101.78 °C of the original to 60.13 °C of the processed sample. SEM images for the cellulose (processed and unprocessed) shows the status and fiber–fiber alignment and its orientation with each other. Finally cavitation has proved to be very efficient tool for reduction in size from millimeter to nano scale for highly crystalline materials.     

Reservoir Pore Structure Classification Technology of Carbonate Rock Based on NMR T 2 Spectrum Decomposition

The carbonate reservoir has a number of properties such as multi-type pore space, strong heterogeneity, and complex pore structure, which make the classification of reservoir pore structure extremely difficult. According to nuclear magnetic resonance (NMR) T ₂ spectrum characteristics of carbonate rock, an automatic pore structure classification and discrimination method based on the T ₂ spectrum decomposition is proposed. The objective function is constructed based on the multi-variate Gaussian distribution properties of the NMR T ₂ spectrum. The particle swarm optimization algorithm was used to solve the objective function and get the initial values and then the generalized reduced gradient algorithm was proposed for solving the objective function, which ensured the stability and convergence of the solution. Based on the featured parameters of the Gaussian function such as normalized weights, spectrum peaks and standard deviations, the combinatory spectrum parameters (by multiplying peak value and normalized weight for every peak) are constructed. According to the principle of fuzzy clustering, the carbonate rock pore structure is classified automatically and the discrimination function of each pore structure type is obtained using Fisher discrimination analysis. The classification results were analyzed with the corresponding casting thin section and scanning electron microscopy. The study shows that the type of the pore structure based on the NMR T ₂ spectrum decomposition is strongly consistent with other methods, which provides a good basis for the quantitative characterization of the carbonate rock reservoir pore space and lays a foundation of the carbonate rock reservoir classification based on NMR logging.     

Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds

Two hexanuclear niobium halide cluster compounds with a [Nb₆X₁₂]²⁺ (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable B_o field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of ⁹⁵Mo nuclei in structurally related compounds containing [Mo₆Br₈]⁴⁺ cluster cores. Experimentally determined δ_iso(⁹³Nb) values are in the range from 2400 to 3000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (V_zz and δ₃₃) coinciding with the molecular four-fold axis of the [Nb₆X₁₂]²⁺ unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (V_zz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (V_yy) and the largest CS principal axis (δ₁₁) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by ^79/81Br NQR and ³⁵Cl solid-state NMR measurements.     

Magnetic field distribution in superconducting niobium by nuclear magnetic resonance fourier spectroscopy

Nuclear magnetic resonance measurements of the superconducting mixed-state field distribution in niobium metal are reported. It is demonstrated that pulsed NMR Fourier spectroscopy (defined in the text) can resolve considerable detail in the field distribution functionf(h). A simple analytic model forf(h) was used for numerical calculation of the expected spectrum shape. An ordered vortex lattice was always observed. Far from the transition the spectra were most consistent with triangular lattice symmetry. The temperature variation of the Maki parameter? ₂ was measured. The shift of spectrum position is compatible with appreciable reduction of spin susceptibility in the superconducting state.     

On the microwave absorption of superconducting Nb3Sn

Measurements ofdc-resistance, surface resistance at 9.6 GHz and x-ray diffraction were made on Nb₃Sn layers having thicknesses between 4 and 7 μ. Samples were prepared by condensing tin on niobium foil which was then annealed at high temperature. This process was repeated, in some cases as many as twenty times. The best samples showed steep transition curves close to 18.2 K. X-ray measurements indicated a high degree of stoechiometry. The surface resistance decreased from 5 · 10^?2Ω atT _c to a residual value of 3 · 10^?4 Ω. This relatively high value can be due to minor deviations from stoechiometry or possibly to similar mechanisms as proposed for pure elements.     

Niobium based coatings for dental implants

Niobium based thin films were deposited on stainless steel (SS) substrates to evaluate them as possible biocompatible surfaces that might improve the biocompatibility and extend the life time of stainless steel dental implants. Niobium nitride and niobium oxide thin films were deposited by reactive unbalanced magnetron sputtering under standard deposition conditions without substrate bias or heating. The biocompatibility of the surfaces was evaluated by testing the cellular adhesion and viability/proliferation of human cementoblasts during different culture times, up to 7 days. The response of the films was compared to the bare substrate and pieces of Ti6Al4V; the most commonly used implant material for orthopedics and osteo-synthesis applications. The physicochemical properties of the films were evaluated by different means; X-ray diffraction, Rutherford backscattering spectroscopy and contact angle measurements. The results suggested that the niobium oxide films were amorphous and of stoichiometric Nb₂O₅ (a-Nb₂O₅), while the niobium nitride films were crystalline in the FCC phase (c-NbN) and were also stoichiometric with an Nb to N ratio of one. The biological evaluation showed that the biocompatibility of the SS could be improved by any of the two films, but neither was better than the Ti6Al4V alloy. On the other hand, comparing the two films, the c-NbN seemed to be a better surface than the oxide in terms of the adhesion and proliferation of human cemetoblasts.     

Calculation of Chemical Shifts of X-Ray-Emission Spectra of Niobium in Niobium(V) Oxides Relative to Metal

Chemical shifts of the K_α1 and K_β1 lines of X-ray-emission spectra of niobium in oxides (Nb₂O₅)_n, n = 1–4, relative to metal Nb have been calculated. Stoichiometric clusters (Nb2O5)n the electronic structure of which was calculated using accurate relativistic pseudopotentials and two-component version of the density functional theory are considered as prototypes for modeling different crystal forms of niobium(V) oxide. The chemical shifts were calculated using the method based on using the property of approximate proportionality of valence spinors in the core region of the heavy atom [11]. Corrections to values of chemical shifts have been determined with allowance for deviations from the abovementioned proportionality. Rapid convergence of results with respect to the size of the niobium oxide cluster has been demonstrated.     

Interfacial Properties of Phosphate Glass Fiber/Poly(caprolactone) System Measured Using the Single Fiber Fragmentation Test

Phosphate glass fiber of the composition 20Na₂O–24MgO–16CaO–40P₂O₅ was produced using an in-house fiber drawing rig. The interfacial properties of the phosphate glass fiber/poly(caprolactone) (PCL) system were measured using the single fiber fragmentation test (SFFT). The system was calibrated using E-glass fibers and polypropylene system. This gave an interfacial shear strength (IFSS) of 4.1 MPa, which agrees well with other published data. The IFSS for the unsized (as drawn) phosphate glass fiber/PCL system was found to be 1.75 MPa. Fibers treated with 3-aminopropyl-triethoxy silane (APS) showed an IFSS of 3.82 MPa. X-ray photoelectron spectroscopic (XPS) analysis of unsized and silane sized fibers established the presence of silane on the fiber surface. Degradation tests of the silane treated fiber/PCL samples were carried out in deionised water at 37°C and it was found that the IFSS values decreased over time. Four others silanes were also investigated but APS gave the highest IFSS values.     

The effect of gradient sampling schemes on diffusion metrics derived from probabilistic analysis and tract-based spatial statistics

Purpose

The purpose was to systematically evaluate the effect of diffusion gradient encoding scheme on estimated fractional anisotropy (FA), mean diffusivity (MD) and the voxel-wise probability of identifying crossing fibers in the brain.

Materials and Methods

Eight healthy volunteers (mean age 26.5±1.3 years, 5 males, 3 females) were imaged using a Spin-Echo Echo-Planar-Imaging sequence acquired with two signal averages [number of signals averaged (NSA)], 127 diffusion directions, and b-values of 750 s/mm² and 1500 s/mm². The number of diffusion gradient directions (N_d) was reduced from the original value whilst maintaining a homogeneous gradient distribution enabling direct comparison of subsampled data sets with N_d=15, 28, 43, 84, 112 and 127. FA and MD maps were generated and analyzed using tract-based spatial statistics. Effect of N_d on estimated FA and MD was tested with voxel-wise statistics in 13 regions of interest. The number of voxels supporting two fiber populations (NV²) at different N_d values was estimated using Bayesian estimation of diffusion parameters.

Results

Low FA values decreased significantly with increasing N_d and with increasing NSA. MD was only marginally sensitive to N_d and NSA. NV₂ increased significantly with N_d but not with NSA. Thus, we conclude that accurate estimation of standard diffusion metrics FA and MD is mainly dependent on the signal-to-noise ratio (SNR), whereas the ability to differentiate multiple fiber populations requires a high diffusion sampling density.     

A universal route for the simultaneous extraction and functionalization of cellulose nanocrystals from industrial and agricultural celluloses

A simple route was designed to extract the cellulose nanocrystals (CNCs) with formate groups from industrial and agricultural celluloses like microcrystalline cellulose (MCC), viscose fiber, ginger fiber, and bamboo fiber. The effect of reaction time on the microstructure and properties of the CNCs was investigated in detail, while microstructure and properties of different CNCs were compared. The rod-like CNCs (MCC) with hundreds of nanometers in length and about 10 nm in width, nanofibrillated CNCs (ginger fiber bamboo fiber) with average width of 30 nm and the length of 1 μm, and spherical CNCs (viscose fiber) with the width of 56 nm were obtained by one-step HCOOH/HCl hydrolysis. The CNCs with improved thermal stability showed the maximum degradation temperature (T _max) of 368.9–388.2 °C due to the introduction of formate groups (reducibility) and the increased crystallinity. Such CNCs may be used as an effective template for the synthesis of nanohybrids or reinforcing material for high-performance nanocomposites.     

Charge-density waves in Nb1 + xS2 crystals

In-situ intercalation of surplus niobium during heating of 3R-Nb_{1 + x}S₂ (x ≥ 0.09) layered crystals in ultra-high vacuum up to 1500 K triggered an unusual inter-polytypic transition from a trigonally prismatic coordinated polytype into an octahedrally coordinated one. The new polytype contains charge-density waves with a commensurate-incommensurate phase transition, temperature-dependent on the intercalated niobium concentration. Charge-density waves in the Nb_{1 + x}S₂ compound, observed for the first time here, were studied by transmission electron diffraction and scanning tunnelling microscopy.     

Low-temperature STM/STS studies on boron-doped (1 1 1) diamond films

We have performed scanning tunneling microscopy/spectroscopy (STM/STS) experiments on (1 1 1)-oriented epitaxial films of heavily boron-doped diamond (T_c∼5.4 K). We present that tunneling conductance spectra show temperature-dependent spatial variations. In the low-temperature region (T=0.47 K), the tunneling spectra do not show strong spatial dependence and a superconducting energy gap is observed independent of the surface morphology. In the high-temperature region (T=4.2 K), on the other hand, the tunneling conductance spectra show significant spatial dependence, indicating the inhomogeneous distribution of the superconducting property due to the distribution of boron atoms.     

Laser surface treatment of regenerated cellulose fiber

Effects of the excimer laser irradiation on regenerated cellulose fibers were investigated. The surface structure change was remarkable only when the ArF laser was applied. Small pores and fibrils were observed on the fiber surface at the high fluence irradiation. In some cases, several cracks were observed inside the fiber. The fiber structure change was strongly dependent on fluence and number of pulses. XPS analysis indicated an increase of carbonyl groups and removal of CO and CO₂ on the fiber surface. Concerning the fiber properties, the tensile strength lowered, and the moisture content was improved a little. Those property changes could be explained by the breakage of intermolecular hydrogen bonding and that of the main chain of the cellulose molecule. Increase of specific surface area and chemical structure change suggest that irradiated fiber can be applied as a component for soft composite materials.     

Quantitative NMR microscopy on intact plants

Quantitative high resolution images on intact young maize plants were acquired by using magnetization-prepared NMR microscopy. Although the spatial resolution is low compared with that of light microscopy, the calculated spin density and T₁ maps exhibit contrasts that are in excellent agreement with photomicrographic images. The T₂ map gives image contrasts that are not visible in a usual light microscopic image. The diffusion images show an anisotropic behavior of the water self-diffusion coefficient in the vascular bundles, which can be understood by the cell morphology in this plant section. This work demonstrates that quantitative imaging on intact plant systems is possible and that long total acquisition times are no obstacle. Furthermore, the different single parameter maps give a better insight into the morphology of plants under in vivo conditions.