Investigation of short range ordering in polymers by means of radial distribution functions derived from X-ray diffraction

Four samples of polyethylene terephthalate (PET), with different thermal histories were investigated by radial distribution function (RDF) methods. Intramolecular distances in the polymer repeat unit were successfully attributed to peaks in the RDF plot up to values of r 5 Å. A broad peak at 4 Å was attributed to nearest neighbour intermolecular ordering, but there was no evidence of ordering beyond this distance in samples annealed for prolonged periods at temperatures close to the polymer T _g. This evidence does not support previous models proposing the presence of extensive para-crystalline ordering in amorphous PET. Low frequency broad peaks, with a periodicity of 4 Å, were resolved out to values of r 20 Å in the RDF plot for a sample with a density crystallinity index of 20%, thus confirming the sensitivity of the RDF analysis to short range intermolecular ordering.     

The structure of amorphous aluminium phosphate by radial distribution functions derived from X-ray diffraction

An investigation of the molecular structure of amorphous aluminium phosphate, prepared from a recently discovered complex (AlPO₄ · HCl · 4C₂H₅OH), has been carried out using radial distribution function (RDF) techniques. Studies were made on two samples, one prepared by decomposing the solid complex and the other from powder produced by evaporating to dryness a solution of the complex in methanol and then decomposing and grinding the solid obtained. RDF curves were obtained from both samples, and were found to closely resemble that previously reported for vitreous silica. The short range order in both samples is similar to that in vitreous silica, with aluminium and phosphorous atoms occupying positions in aluminium phosphate similar to the positions of silicon atoms in silica. This structure is consistent with the crystal chemistry of aluminium phosphate.It is possible to assign all the peaks in the RDF plots out to values of r5 Å to known inter-atomic distances. The peak at 1.6 Å represents the Al-O and Al-P bond lengths, and is broader than the corresponding Si-O peak in vitreous silica, as the Al-O and P-O bonds are respectively slightly longer (Al-O) and shorter (P-O) than the equivalent Si-O bonds. Subsequent peaks result from the O-O distances ( 2.6 Å); the Al-Al, Al-P and P-P distances ( 3.1Å); the Al-second O and P-second O distances ( 4.2 Å), and O-second O, Al-second Al, P-second P and Al-second P distances ( 5.0 Å). The sample prepared from the methanolic solution shows some small additional peaks in the region 4 to 5 Å, indicating more order in the second neighbour distances.Analysis of the P-O and Al-O peak area indicates that both P and Al atoms are co-ordinated to four network oxygen atoms at a distance 1.6Å, and that absorbed water also co-ordinates to one or both atoms with a P-O and/or Al-O distance of 1.6 Å.     

High resolution TEM study of ceramic BaO·Pr2O3·4TiO2

Ceramic specimens of BaO·Pr₂O₃·4TiO₂ (Ba_4.5Pr₉Ti₁₈O₅₄) were prepared by the mixed oxide-route. The single phase products were examined by High Resolution Transmission Electron Microscopy (HRTEM). Orthorhombic symmetry, with cell parameters a22.2 Å, b12.2 Å and c7.6 Å, was confirmed. On the basis of space group pnam (No. 62) and the crystal structural data of Rawn et al., good agreement was obtained between the experimental HRTEM images and images simulated by the multislice method.     

Simultaneous measurement of surface tension and kinematic viscosity using thermal fluctuations

We have developed a surface laser-light scattering apparatus to measure simultaneously surface tension and kinematic viscosity. In this method, we can obtain the surface properties by the laser heterodyne detection of light scattered from thermally excited capillary waves (called ripplon), which are typically of low amplitude (1 nm) and a characteristic wavelength (100m). Two gratings (d=100 and 200m) were employed to select the wave number of the capillary waves and to produce a reference beam for heterodyne detection. It was found through an experimental study on water that this contact-free method has considerable potential for application to measurements under extreme conditions such as high temperatures and high pressures.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

Sol-gel prepared Ni-alumina composite materials

The sol-gel method has been utilized for the preparation of dense, homogeneous ceramic-metal composites with up to 50% Ni in Al₂O₂. Examination by SEM and TEM shows that the materials consist of micrometre-size Al₂O₃ with metallic Ni in isolated regions from 50 m down to nanometre size. The density ranges from 97% (10% Ni) to 74% (50% Ni) of the theoretical number. The hardness decreases from 18 GPa for pure alumina to 10 GPa for alumina containing 50% Ni. The fracture toughness increases significantly from K _1c=3–4 MPa m^1/2 to K _1c=8.5 MPa m^1/2. The elastic and shear moduli decrease from E=400 GPa and G=160 GPa for pure alumina to E=320 GPa and G=135 GPa when containing 50% Ni. The electrical resistivity is 10⁶m with 10 to 40% Ni but decreases drastically at 50% Ni content.     

On crystal alignment in polycrystalline YBCO materials based on TEM observation

Previously, we have observed that parallel lattice fringes show up regularly in MTG samples, indicative of good alignment of unit cells in strips of size 100 nm × a few times 100 nm. We have prepared films ( 80 nm) for TEM observation using YBCO material fabricated by the conventional solid-state reaction method in order to study the crystal texture in a length scale from a few 100 nm down to 3 Å. Parallel lattice fringes are observed to stretch across a cross-section 0.3×0.5 m². Cross lattice fringes intersecting at 90° and 45° are observed as rare events. This result suggests that the degree of alignment in the crystal texture is higher than expected inside a grain of size a few m.     

Structure of alkali dimers at the surface of liquid helium

Calculations are presented of the equilibrium configuration (dimple) of a Na₂ or Li₂ molecule absorbed on the surface of liquid³H e or liquid⁴He. The computed aimer binding energies are somewhat greater than those of the monomers. The lowest energy occurs when the molecule lies flat, but the energy in the erect orientation is only 1K higher (implying relatively free rotation). The center of mass lies 4Åabove the liquid surface and the dimple has a depth 3Å. An exceptional case is Li₂ on liquid³H e, for which the surface state is unstable relative to solvation in the bulk.     

Stability of nickel coated sapphire whiskers

The effect of high temperature annealing (1100 to 1300° C) on the stability of nickel coated purified sapphire whiskers has been investigated. It was found that the initially coherent coating spheroidized to form a series of partially adherent nickel particles, which increased in size with continued time at temperature. The time for complete adhesion of the particles, which was established from the product of the number and volume of particles per unit area of surface, decreased from 72 h at 1100° C to 3 h at 1300° C, giving an activation energy of 70 kcal/mol. In addition at 1300° C, after 8 h, there was evidence for whisker breakdown from a sapphire-nickel reaction.     

Limits on Superconductivity in Nanoparticles and Nanowires

Recent experimental results are consistent with the prediction that superconductivity is suppressed in aluminum nanoparticles which are so small (10 nm diameter) that the electronic energy level spacing exceeds the superconducting energy gap in bulk material. Very recent experiments on nanowires (diameter 5–10 nm, length 150 nm) of MoGe indicate that a dissipative phase transition between superconducting and normal behavior occurs when the normal resistance of the wire equals the superconducting quantum resistance h/4e² 6.5 k.     

Particle size control of 1,3,5-triamino-2,4,6-trinitrobenzene by recrystallization from DMSO

Batches of up to 46g of the insensitive explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) have been recrystallized from DMSO in an effort to prepare larger particle-size material for recycling previously-used TATB and also for use in special formulations. The first part of the study investigated the conditions required to shift the particle-size distribution maximum from 50–70 m to several hundred micrometres in diameter. Distributions peaking at 200–246 m were successfully produced by varying the cooldown rate and degree of agitation during cooling. The second part of the study emphasized regeneration of the standard 50–70 m distribution from submicron size (ultrafine TATB) particles. The distributions peaking at 76–88 m, 27–31 m, and 15–17 m, successfully bracketed the target particle sizes, were grown by changing the degree of solution saturation. The choice of saturation temperature for the TATB/DMSO solution was based on earlier small-scale recrystallization and solubility work.     

CO/pH2: A Molecular Thermometer

We utilize reversible temperature dependent changes in the IR absorption spectrum of CO molecules isolated in solid parahydrogen (pH₂) to probe bulk temperature changes during rapid vapor deposition. The intensity of a well resolved feature near 2135 cm^–1 increases monotonically with temperature over the 2 to 5 K range. The thermally populated initial state of this transition lies 12 K above the CO/pH₂ ground state. During the deposition of 100 ppm CO/pH₂ samples, we detect temperature gradients 10 K/cm in 0.1 cm-thick samples subjected to heat loads 10 mW/cm². The resulting estimated thermal conductivity (TC) is 3(±2) mW/cm-K, averaged over the 2 to 5 K region. This value is 1000 times lower than the TC of single crystal solid pH₂, and 10 times lower than previously measured for pH₂ solids doped with 100 ppm concentrations of heavy impurities [Manzhelii, Gorodilov, and Krivchikov, Low Temp. Phys. 22, 131 (1996)]. We attribute this abnormally low TC to the known mixed fcc/hcp structure of the rapid vapor deposited solids.     

Thermal expansion of interlayer spacing and thermal vibrational displacement of carbon atoms in petroleum coke

On petroleum coke heat-treated at various temperatures in the range from 1600 to 3000°C, thermal expansion of the interlayer spacing and the mean-square displacement along the c-axis due to thermal vibration of carbon atoms were measured from room temperature to 1050°C by means of X-ray diffractometry. The static mean-square displacement due to imperfect crystallization was also estimated for each sample.The c-axis spacing increases linearly with temperature and the slopes had almost the same values (1.85×10^–4 to 1.89×10^–4Å/°C) for all samples. The mean-square thermal vibrational displacements of carbon atoms increased almost linearly from 0.012Ų at room temperature to 0.047Ų at 1000°C for all samples, except for the sample heat-treated at 1640°C.A mean free space between the layer planes, that is the interlayer spacing minus twice the total root-mean-square displacement of carbon atoms along the c-axis direction, was obtained in consideration of the mean-square thermal vibrational displacement and the mean-square static displacement. The mean free space increases abruptly with decrease of c-spacing from 6.86 to 6.85Å (heat-treatment temperatures of 1640 and 2100°C respectively), then decreases slowly and eventually again begins to increase with further decrease of c-axis spacing to 6.73Å.     

The frictional behaviour of LiF single crystals

A study has been made of the influence of initial surface roughness, renewable and non-renewable surface contaminants, and irradiation hardening on the coefficient of friction for one LiF single crystal (A) sliding on another (B) in {100}_A<010>_A{100}_B 010_B orientation at 295 K. The normal load was 1 N, the nominal contact pressure 0.1 MPa, the sliding velocity 0.2 to 0.6 mm sec^–1, and the amplitude of the (reciprocate) motion a few millimetres. Any influence of non-renewable contaminants persisted only for cumulative relative displacements 0.1 m, and that of micrometre-scale initial surface roughness only for a few metres. At steady state in the presence of renewable contaminants the coefficient of friction varied only from a high of 0.45 in ultra-high vacuum ( 7.5 × 10^–8 Pa) and dry nitrogen-rich air ( 10⁵ Pa, relative humidity 15%) to a low of 0.38 in moist nitrogen-rich air ( 10⁵ Pa, relative humidity 50%). Irradiation hardening had no effect on the coefficient of friction at steady state. The worn surfaces created by steady-state sliding always exhibited a grooved topography partly obscured by more-or-less adherent layers of variously consolidated equiaxed debris particles 100 nm in size. Owing to the action of image forces, these particles contained no dislocations. It is suggested that the coefficient of friction was determined at steady state by the stress needed to shear these tiny particles past one another as near-rigid bodies.     

Some observations on the deformation characteristics of bulk polycrystalline zirconium hydrides

The deformation behaviour of bulk polycrystalline zirconium hydrides in the composition range ZrH_1.27 to ZrH_1.66 has been investigated by compressive loading at temperatures between room temperature and 500° C. Single-phase -zirconium hydride is brittle below 100° C. Analyses of slip traces on specimens deformed at temperatures between 100 and 250° C have shown that the glide planes are {111} types. The deformation characteristics of and ( + ) alloys at temperatures between 100 and 500° C are consistent with the hydrogen vacancies in the -phase providing significant lattice friction to the movement of dislocations in the zirconium lattice of the hydride structure. The room temperature fracture stress of ( + ) alloys increases with the volume fraction of the -phase and this can be related to the resistance offered by platelets to the propagation of cleavage cracks in the matrix. In a ( + + ) alloy the resistance to crack propagation at room temperature is further increased by the soft -zirconium phase.     

Preparation and analysis of high-T c Nb-Ge films

The dependence of T_c on sputtering conditions, chemical composition, and phase structure for Nb-Ge films has been studied. It was found that T_c varied with composition, but was not dependent on exact stoichiometry of the film; the Nb/Ge ratio was <3 for very high T_c 23 K films and 4 for films with T_c 20 K. X-ray results showed that the films with T_c 23 K contained a certain amount of tetragonal Nb₅Ge₃ with a lattice parameter of A15 phase 5.14 Å. The depth profile of very high T_c films showed no increase of oxygen concentration at the film-substrate interface; no correlation of high T_c and impurities was found.     

Vortex imaging in superconducting films by scanning hall probe microscopy

We have used a low noise Scanning Hall Probe Microscope (SHPM) to study vortex structures in superconducting films. The microscope has high magnetic field (2.9×10^–8T/Hz at 77K) and spatial resolution, 0.85m. Magnetic field profiles of single vortices in High T_c YBa₂Cu₃O_7– thin films have been successfully measured and the microscopic penetration depth of the superconductor has been extracted as a function of temperature. Flux penetration into the superconductor has been imaged in real time (8s/frame).     

The constitution of the Ni-Al-Ru system

The constitution of the Ni-Al-Ru system has been investigated in the range 0 to 50 at% Al. Isothermal sections at 1523 and 1273 K have been determined using microstructural observations, electron probe microanalysis and X-ray diffraction. The phases present were: nickel-based solid solution (); (based on Ni₃Al); solid solutions based on NiAl and RuAl, respectively (designated ₁ and ₂), and ruthenium-based solid solution (Ru). The maximum solubility of Ru in was 5 at%. ₁, and ₂ show extensive range of solubilities, namely up to 20at% Ru in ₁ and up to 25 to 35 at% Ni in ₂. Three-phase equilibrium between , ₂ and (Ru) existed at 1523 and 1273 K. Also at 1523 K, three-phase equilibria existed between , and ₁ and ,₁ and ₂, while at 1273 K, the equilibria were between , ₁,₂ and , , ₂ indicating the occurrence of a reaction +₁, +₂ at a temperature between 1523 and 1273 K. Liquidus features have been deduced from data on as-solidified structures. Lattice parameter data and hardnesses are also reported.     

Low temperature internal friction on γ-irradiated polyvinylidene fluoride (PVDF)

A least-squares fitting of the below room temperature part of the internal friction spectra, obtained by the torsion pendulum technique on as-received and-irradiated (up to 1 Grad) strips and fibres of polyvinylidene fluoride [-(CH₂-CF₂-) _n -.; PVDF] by a superposition of single Debye functions, reveals that the spectral component features are determined not only by purely amorphous chain characteristics but also by the dosedependence of crystallinity. A careful analysis of the relaxation spectra confirms that at least one relaxation effect (236 K) is created upon irradiation. The analysis of the dose dependence of the characteristics of the (glass transition; 220 K) and _u (apparent upper glass transition; 270 K) relaxations, suggests the probable influence of crystallinity on the molecular motion in the amorphous phase. The increase of the intensity of the relaxation (190 K) is related to the irradiation-induced crystallite degradation.Fellow of the Interuniversitair Instituut voor Kernwetenschappen     

Pseudogap Behavior in the Electronic Specific Heat of La2−xSrxCuO4

In La214, the electronic specific heat coefficient (=C _el /T) is gradually suppressed with lowering T below a certain temperature T* (> T _c ), where the in-plane resistivity and magnetic susceptibility also tend to be suppressed slightly. Temperature T*, increasing with lowering x, is in qualitative agreement with the mean field T _c (T _co ), estimated from the superconducting gap amplitude 2 _o at T T _c , as the onset temperature T* of a pseudogap in Bi2212. The gradual suppression of below T _co implies that a pseudogap will also open up below T _co in La214 as in Bi2212. In underdoped samples, whose pseudogap-like behaviors in C _el(T) become marked, the anomaly of C _el around T _c is rather different from the BCS expectation.     

Microstructure and mechanical properties of rapidly quenched L20 and L20+L12 alloys in Ni-Al-Fe and Ni-Al-Co systems

Ductile L2₀-type wires and+L1₂-type duplex wires with high strengths and large elongation in the Ni-Al-Fe and Ni-Al-Co ternary systems have been manufactured directly from the liquid state by an in-rotating-water spinning method. The wire diameter was in the range 80 to 180m and the average grain size was 2 to 4m for the wires and 0.2 to 1.0m for the+ wires. _y, _f and _p of the wires were found to be about 360 to 760 MPa, 560 to 960 MPa, and 0.2 to 5.5%, respectively, for the Ni-Al-Fe system, those of the+ wires were about 395 to 660 MPa, 670 to 1285 MPa, and 3.5 to 17%, respectively, for the Ni-Al-Fe system, and about 260 to 365 MPa, 600 to 870 MPa, and 4.0 to 7.0%, respectively, for the Ni-Al-Co system. Cold-drawing caused a significant increase in _y and _f and the values attained were about 1850 and 2500 MPa, respectively, for Ni-20Al-30Fe and Ni-25Al-30Co wires drawn to about 90% reduction in area. The high strengths, large elongation and good cold-workability of the melt-quenched and+ compound wires have been inferred to be due to the structural change into a low-degree ordered state containing a high density of phase boundaries, suppression of grain-boundary segregation and refinement of grain size.