Scanning probe microscopy study of exfoliated oxidized graphene sheets

Exfoliated oxidized graphene (OG) sheets, suspended in an aqueous solution, were deposited on freshly cleaved HOPG and studied by ambient AFM and UHV STM. The AFM images revealed oxidized graphene sheets with a lateral dimension of 5–10 μm. The oxidized graphene sheets exhibited different thicknesses and were found to conformally coat the HOPG substrate. Wrinkles and folds induced by the deposition process were clearly observed. Phase imaging and lateral force microscopy showed distinct contrast between the oxidized graphene and the underlying HOPG substrate. The UHV STM studies of oxidized graphene revealed atomic scale periodicity showing a (0.273 ± 0.008) nm × (0.406 ± 0.013) nm unit cell over distances spanning few nanometers. This periodicity is identified with oxygen atoms bound to the oxidized graphene sheet. I(V) data were taken from oxidized graphene sheets and compared to similar data obtained from bulk HOPG. The dI/dV data from oxidized graphene reveals a reduction in the local density of states for bias voltages in the range of ±0.1 V.     

Spin glasses on thin graphs

In a recent paper [C. Baillie, D.A. Johnston and J.-P. Kownacki, Nucl. Phys. B 432 (1994) 551] we found strong evidence from simulations that the Ising antiferromagnet on “thin” random graphs — Feynman diagrams — displayed a mean-field spin-glass transition. The intrinsic interest of considering such random graphs is that they give mean-field theory results without long-range interactions or the drawbacks, arising from boundary problems, of the Bethe lattice. In this paper we reprise the saddle-point calculations for the Ising and Potts ferromagnet, antiferromagnet and spin glass on Feynman diagrams. We use standard results from bifurcation theory that enable us to treat an arbitrary number of replicas and any quenched bond distribution. We note the agreement between the ferromagnetic and spin-glass transition temperatures thus calculated and those derived by analogy with the Bethe lattice or in previous replica calculations.

We then investigate numerically spin glasses with a ±J bond distribution for the Ising and Q = 3, 4, 10, 50 state Potts models, paying particular attention to the independence of the spin-glass transition from the fraction of positive and negative bonds in the Ising case and the qualitative form of the overlap distribution P(q) for all of the models. The parallels with infinite-range spin-glass models in both the analytical calculations and simulations are pointed out.     

High-resolution gamma-ray spectroscopy of ΛLi

We report on the first observation of hypernuclear γ transitions using germanium detectors. Using a large-acceptance Ge detector system, we observed two γ transitions in _Λ⁷Li, the spin-flip transition at 689±4keV and the transition at 2050±2 keV (preliminary). The strength of the ΛN spin-spin interaction is derived from the energy of the former transition. As for the latter transition, B(E2) was measured to be 3.9±0.6±0.4 e²fm⁴ (preliminary), which indicates a shrinkage of the nuclear size of _Λ⁷Li from ⁶Li and confirms “glue-like role” of Λ.     

Phase evolution during the melting and recrystallization of ceramic core in the (Bi,Pb)-2223 tape

The phase evolution during melting and recrystallization of (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ ((Bi,Pb)-2223) core in a Ag-sheathed monofilamentary tape has been investigated. The tape was fabricated by PIT process with powders containing nearly pure (Bi,Pb)-2223 phase. Short samples were melted at 805 °C, 808 °C, 812 °C, 816 °C, 831 °C, slowly cooled at 1.5 °C/h under flowing 1.6% O₂ balanced with argon and quenched in air at room temperature. X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) were applied for the phase identification. The results show that (Bi,Pb)-2223 core is partially melted into a liquid and alkaline earth cuprates (AECs), mainly 2:1-AEC, at 805 °C, 808 °C, 812 °C, and well reforms directly from the melt during the slow cooling. More (Bi,Pb)-2223 phase is decomposed at temperatures higher than 816 °C, but cannot recrystallize, indicating that a partial melting at some temperatures around a given temperature range is essential to (Bi,Pb)-2223 phase reformation. The melt composition moves from that between “2223” and “2212” stoichiometries towards 2212-like stoichiometry with increasing temperature. This seems to lead to the conclusion that (Bi,Pb)-2223 phase decomposes incongruently into a 2212-like liquid and (Ca,Sr)-cuprates. 2:1-AEC plays the most important role in (Bi,Pb)-2223 melt-recrystallization process. Our results also reveal that plate-like shape (Bi,Pb)-2223 grains can be obtained via melting and recrystallization if the optimum processing conditions are used.     

The structures of sulphur on Pd(111) studied by X-ray standing wavefield absorption and surface EXAFS

The surface structures of R30°-S and R19.1°-S on Pd(111) have been investigated by normal incidence X-ray standing wave (NIXSW) absorption and surface extended X-ray absorption fine structure (SEXAFS). NIXSW measurements show that the most likely site of S adsorption in the R30° phase is the threefold “fcc” hollow. The location of the S atoms at the “fcc” hollow site is consistent with S adsorption on the neighbouring fcc (111) transition metal surfaces. SEXAFS analysis revealed a S–Pd nearest neighbour bond distance of 2.28±0.04 Å. The results for the R19.1° phase suggest that the structure involves a mixed S–Pd overlayer, with the S–Pd vertical layer spacing equal to the Pd bulk 111 spacing.     

The use of polarization modulation and amplitude-sensitive optical heterodyne interferometry for linear birefringence parameters measurement

A novel common-path polarization modulation and amplitude-sensitive optical heterodyne polarimeter is setup in order to characterize a phase retardation plate (PRP) in real time. The phase retardation ΔΦ and fast-axis angle β of the linear birefringence parameters (LBP) of a PRP are measured simultaneously. Meanwhile, the dynamic ranges of 0° < ΔΦ < 180° and 0° < β < 180° are demonstrated experimentally. In order to measure LBP in real time, a polarization modulation is introduced by continuously rotating the tested PRP such that ΔΦ and β are able to be obtained in terms of the ratio of the amplitudes of S polarization and the ratio of P polarization of the heterodyne signals, respectively. Consequently, this novel method, which combines optical heterodyne interferometry with a polarization modulation technique, not only improves the detection sensitivity, but also provides a real time capability to measure LBP. In addition, the error in the LBP measurement is derived and analyzed.     

Development of a 4–15 μm infrared GaAs hyperspectral QWIP imager

In the on-going evolution of GaAs quantum well infrared photodetectors (QWIPs) we have developed a four band, 640 × 512, 23 μm × 23 μm pixel array which we have subsequently integrated with a linear variable etalon (LVE) filter providing over 200 spectral bands across the 4–15.4 μm wavelength region. This effort was a collaboration between NASA’s Goddard Space Flight Center (GSFC), the Jet Propulsion Laboratory (JPL) and the Army Research Laboratory (ARL) sponsored by the Earth Science Technology Office of NASA. The QWIP array was fabricated by graded molecular beam epitaxial (MBE) growth that was specifically tailored to yield four distinct bands (FWHM): Band 1; 4.5–5.7 μm, Band 2; 8.5–10 μm, Band 3; 10–12 μm and Band 4; 13.3–14.8 μm. Each band occupies a swath that comprises 128 × 640 elements. The addition of the LVE (which is placed directly over the array) further divides the four “broad” bands into 209 separate spectral bands ranging in width from 0.02 μm at 5 μm to 0.05 μm at 15 μm. The detector is cooled by a mechanical cryocooler to 46 K. The camera system is a fully reflective, f/4.2, 3-mirror system with a 21° × 25° field of view. The project goals were: (1) develop the 4 band GaAs QWIP array; (2) develop the LVE and; (3) implement a mechanical cryocooler. This paper will describe the efforts and results of this undertaking with emphasis on the overall system characteristics.     

Oxygen induced reconstruction of (h11) and (100) faces of copper

A LEED and AES study on oxygen adsorption on Cu(100) and (h11) faces with 5 h 15 has been performed under various adsorption conditions (220 K T 670 K and 1 × 10⁻⁸ P 6 × 10⁻⁵ Torr of oxygen). The dependence of adsorption temp on the oxygen surface superstructures is pointed out. At least, three oxygen surface states exist on a Cu(100) face. For low temperature exposures to oxygen, under conditions of slow surface diffusion, on the (100) face, two oxygen surface phases exist: a “four spots” and a c(2 × 2) superstructure, both observed even at saturation coverage; on all the stepped faces, a c(2 × 2) appears and no faceting is observed. For high temperature exposures, on the (100) face, two oxygen superstructures are observed, a “four spots” followed by a (2√2 × √2)R45° at higher coverages; on all the stepped faces, surface diffusion is activated and oxygen induced faceting occurs. The appearance of faceting is associated with the onset of the formation of the (2√2 × √2)R45° structure on the (100) face. The oxygen induced faceting and the oxygen surface meshes are reversible with coverages. At saturation coverage, a non-reversible surface transition between the c(2 × 2) and (2√2 × √2)R45° superstructures is observed at 420 ± 20 K. The importance of impurity traces on the surface meshes is emphasized. Oxygen coverage at saturation is independent of the studied faces and adsorption temperature. Faceting occurs at a critical coverage value, whatever the stepped faces and adsorption temperature are. Models of the oxygen structure on the (h10) stepped faces are discussed.     

The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.     

Surface morphology, chemical contrast, and ferroelectric domains in TGS bulk single crystals differentiated with UHV non-contact force microscopy

Ferroelectric bulk single crystals of tri-glycine sulphate (TGS) have been investigated in ultra-high vacuum (UHV) using dynamic force microscopy (DFM) in the non-contact (nc) mode. Both chemical contrast from different sub-unit cell cleavage steps, and ferroelectric domains were differentiated by recording the variation in interaction force affecting the excitation amplitude A_exc applied to the piezo shaker in constant amplitude DFM. No chemical difference was found for steps measuring half the unit cell height b, in contrast to b/4—steps where sulphate ions change the local short-range chemical forces. By varying the bias voltage applied to the TGS counter electrode, the sign of bound surface charge within each ferroelectric domain was determined. Domain walls separating regions with antiparallel polarisation vectors are resolved down to a 9 nm domain wall width. Furthermore, we achieved atomic resolution with nc-DFM on cleaved TGS samples indicating the monoclinic unit cell at the ferroelectric sample surface with a=1.0±0.05 nm, c=0.55±0.05 nm, and β=107±3°.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part I: primary experimental results

ε-caprolactam (CL) polymerization to polyamide-6 (Nylon 6) was studied at different contents of water in CL (0.01–2 wt%), with or without ε-amino-caproic acid (ACA) as an activator, applying to the mixture an initial treatment of Ultrasound (US) (17.5–20 kHz) at low temperatures (70–110 °C) and for short times (max 10 min). It was verified that polymerization at 260 °C produces a polymer having a much higher molecular weight (MW) when US is applied with respect to silent (SIL) conditions i.e. without the use of ultrasound. This constitutes a “pre-sonication effect”. The ratio (MW)_US/(MW)_SIL is inversely proportional to the initial content of water in CL. The action of US converts CL at very low temperatures (70–110 °C) and water content, in comparison with silent conditions where CL was unconverted.

Optimized conditions are studied with respect to nature and pressure of gas inside the reactor, temperature, time and frequency of US irradiation, energy consumption and nature of activator.     

Impurity effects on adhesive energies

Some simple arguments are made about the effect of impurities on adhesive interactions at solid junctions. A universal adhesive force relation is derived for brittle adhesion. The adhesive binding energy, ΔE, is an important parameter in brittle adhesion forces. ΔE has also been shown by others to be important when there is plastic flow. We found that impurity effects on ΔE are determined by the segregation energies to the junction and to the free surfaces. At low temperatures, if it is energetically more favorable for impurities to segregate to the surfaces than to the junction, then the impurities will decrease ΔE. The converse is also true. For example, for self junctions which are in registry, ΔE is decreased if surface segregation is exothermic and increased if it is endothermic. These segregation energy relationships are consistent with the results of a number of experiments on the effects of impurities on adhesion forces and grain boundary embrittlement.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part II: additional experiment to understand the "pre-sonication effect"

Ultrasound (US) “pre-sonication effect” is the beneficial effect of US in the hydrolytic polymerization of ε-caprolactam (CL) mixtures with very low water concentrations (about 0.1–1 wt%). It appears after a mild initial treatment of the mixtures with US [17.5–20 kHz, short times (5–15 min), low temperatures (70–110 °C)] followed by heating at 220–260 °C. An explanation is proposed on the basis of the formation in mild conditions (100 °C) of low concentrations of cyclic oligomers never detected in the literature at those conditions. These, under US irradiation, produce linear amino acid oligomers, which are strong activators of polymerization when the mixture of CL and water, after US irradiation, is heated at the suitable polymerization temperature indicated above.     

Nanomechanical probing of microbubbles using the atomic force microscope

Atomic force microscopy (AFM) is a versatile mechanical nanosensor that can be used to quantify the mechanical properties of microbubbles (MBs) and the adhesion mechanisms of targeted MBs.

Mechanical properties were investigated using AFM tipless cantilevers to microcompress the MBs. The range of compressive stiffness for biSphere^® was found to be between 1 and 10 N m⁻¹ using a cantilever with a spring constant of 0.6 N m⁻¹. This stiffness was shown to decrease with the MB size in a non-linear fashion. It is also possible to calculate a theoretical Young’s modulus of the shell.

The adhesion properties of targeted lipid based MBs that use avidin–biotin chemistry for the attachment of targeting ligands were also studied. The MBs were attached to poly-l-lysine treated tipless cantilevers with spring constants ranging from 0.03 to 0.1 N m⁻¹. This system interrogated individual cells with pulling cantilever distance of 15 μm, and scan rate at 0.2 Hz. The depth of contact was not larger than 0.4 μm. The targeted MBs provided a significantly larger adhesion to the cells compared to control ones. Average adhesion force was dependent on depth of contact. Analysis of the data demonstrated a single distribution of adhesion events with median at 89 pN, which is in agreement with the literature for such interactions.

The nanointerrogation of MBs using AFM provides new insight into their mechanical properties, and should be of assistance to MB design and manufacture.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Measurement of the average polarization of B produced by polarized muons in the μ + C → νμ + B reaction

The average polarization of ¹²B produced by the capture of polarized muons in ¹²C has been measured using recoil implantation techniques. From the result we deduce the average polarization of the ¹²B ground state ¹²B(0) corresponding to the ¹²C → ¹²B(0) Gamow-Teller reaction: J_μ(0) = 0.43 ± 0.10. The sizeable deviation of this polarization from the value of 2/3, characteristic of a “bare” 0⁺ → 1⁺ process, is a fair evidence for induced axial-vector interaction(s) in muon capture. The ratio of the induced pseudoscalar and the axial-vector coupling constants is deduced to be: g^μ_P/g^μ_A = 12 ± 5.     

Experimental observation of a copious yield of electrons with small transverse momenta in pp collisions at high energies

Inclusive electron and positron emission have been observed for θ_cm = 30° and S = 2800 GeV² at the CERN Intersecting Storage Rings (ISR). Over the transverse momentum interval 0.2 GeV/c < p_T < 1.5 GeV/c, electrons and positrons, which are equal in number within the experimental accuracies, appear to grow with respect to other particles (pions) approximately like 1/p_T. We are unable to explain their number and p_T-dependence in terms of “conventional” mechanisms.     

Effect of annealing temperature on microstructure of chemically deposited calcium modified lead titanate thin films

Thin ferroelectric films of calcium modified lead titanate Pb_1−xCa_xTiO₃(PCT) have been prepared by chemical deposition process. The as deposited amorphous films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various amounts of calcium (Ca)-doping (0.20, 0.24, and 0.28) on indium tin oxide (ITO) coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out at various annealing temperatures (450, 550, and 650 °C). Characterization of these films by XRD shows that the films exhibit tetragonal phase with perovskite structure. Atomic force microscope images (AFM) are characterized by slight surface roughness with a uniform crack-free, densely-packed structure. Also, Fourier transform infrared spectra (FT-IR) of the as deposited film and annealed thin films (x=0.24) at 650 °C on silicon (Si) substrates were taken to get more information about the film formation. Dielectric studies of the films were carried out and reported.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Excess molar heat capacity of isobutyric acid–water binary liquid mixtures near and far away from the critical temperature

The heat capacity of the liquid–liquid mixture isobutyric acid–water has been measured for the first time near and far away from its critical point using an adiabatic calorimeter. The measurements were performed at atmospheric pressure, in the one phase region as a function of three temperatures: (1) T − T_C = 0.055 °C, (2) T − T_C = 3.055 °C, (3) T − T_C = 8.055 °C and of the composition X in acid (IA). The heat capacity C_p decreases rapidly when X increases at the used temperatures. Near the critical composition, C_p is not affected by the correlation of the concentration fluctuations.

The molar excess heat capacity of the system under investigation was analysed along the phase diagram and considered as a structural transformation effect.