Porous inorganic materials

The field of porous, inorganic materials is experiencing explosive growth, as is shown by more than 6000 literature citations since 1994 along with numerous recent symposia and workshops that have been devoted to this topic. Much of the recent interest has been fueled by new synthetic strategies, such as ‘supramolecular templating’, that have enabled precise engineering of pore size, shape, and connectivity on the mesoscopic scale. In general, template-based approaches involving the cooperative organization of organic—inorganic assemblies as intermediates are emerging as a promising conceptual basis for future developments in the field of porous inorganic materials, such as the synthesis of hierarchical morphologies that mimic the intricate structures found so often in nature.     

Aspects of transition metal mediated polymerizations

Catalysts based on metallocene complexes of early transition metals herald a new era in Ziegler—Natta olefin polymerization. The developments are driven primarily by the flexibility and high activity of metallocene catalysts, which allow excellent control of polymer properties and have led to a remarkably wide spectrum of polymers and copolymers. In-depth mechanistic understanding is proving crucial for catalyst design and has opened up the use of metallocenes in non-Ziegler chemistry, notably as initiators for carbocations polymerizations. Recently developed late transition metal complexes have substantially added to the range of olefin (co)polymers that are now accessible, including copolymerizations with carbon monoxide and polar monomers.     

Modelling materials driven far from equilibrium

Materials driven from equilibrium offer a challenging field for both time and space multiscale modelling. In materials under irradiation the elementary damaging process, that is, the nuclear collision leading to the displacement cascade, is modelled by molecular dynamics (≈ 10 ps, 10³ nm³), whereas the later stage recovery process is modelled by kinetic Monte Carlo (≈ years, 10⁴ nm³); at still a coarser scale, grain boundary segregations are modelled by a meanfield approximation of the very same atomistic model as used in kinetic Monte Carlo modelling. Connecting this broad range of time scales helps to elucidate basic issues on the criteria for alloy stability under irradiation. Irradiation effects on plasticity are beginning to be modelled in the same spirit; a first molecular dynamics study of the interaction of cascade debris with gliding dislocations has been reported together with the first results of mesoscale modelling of dislocation dynamics in the course of a nanoindentation test. Such studies can be extended to materials processed by ball milling.     

Mesoscopic modelling

Mesoscopic modelling covers a wide range of ideas and models. The objective is to study length-scales and time-scales that are not easily accessible to either atomistic or macroscopic continuum methods. ‘Grand-challenge’, large-scale atomistic simulations push at the boundary of the mesoscale at the lower end, while increasing sophistication in micromechanics push at the boundary from the upper end. The increase in computing power is also responsible for the increasing number of 3D as opposed to 2D calculations. Obtaining well-defined, well-validated models remains difficult despite some recent successes.     

Comparative experiments on three-wall and one conventional road vehicle

In 1984 international research took place which compared the transport conditions of quick-frozen foods in thin-wall vehicles and conventional vehicles. This work was done at the request of the group of experts of the UNECE/TRANS/GE.11 in Geneva, Switzerland. In the Netherlands measurements have been carried out on three road vehicles — one conventional and two thin-wall vehicles — in the test station and on the road. The road transport involved taking a commercial cargo of frozen fish from Holland to Italy during the summer (July). Later on an additional test was performed in the test station with a fourth thin-wall vehicle at an ambient temperature of 30°C. The results show, that in the conventional vehicle, equipped with a bulk head and a ceiling air duct, and working on a temperature setting of −25°C, a maximum product temperature of −18°C could be maintained. The maximum temperature difference in the cargo was 6 K. Thin-wall vehicles appeared to have a temperature difference of 12 K between air inlet temperature and warmest product temperature. The maximum product temperature could be held below −12, −15 or −20°C, depending on the air distribution and, in particular, on the cooling power of the thermal appliance.     

Influence of thermomechanical aging on fatigue behaviour of 2014 Al-alloy

The fatigue behaviour of 2014 Al-alloy has been studied in various thermomechanically aged conditions. It is observed that fatigue properties can be improved by a thermomechanical treatment, which would reduce the concentrations of dispersoids, provide a relatively uniform deformation structure and produce fine distribution of θ’ precipitates. Fine θ’ particles inhibit dynamic recovery and produce uniform deformation structure, which improves fatigue behaviour. Presence of dispersoids and coarse precipitate particles leads to the formation of persistent slip bands (PSBs) and a highly heterogeneous deformation structure, which cause damage to fatigue properties.     

Semiconductor strained layers

During the past 25 years (after the growth of the first pseudomorphic GeSi strained layers on Si) we have seen a steady accumulation of new materials and devices with enhanced performance made possible by strain. The past year has been good for strained layers. Until recently, short wavelength (violet to green) and mid-infrared (2–5 μm) regions of the spectrum were not accessible to photonic devices. Short wavelength light emitting diodes and laser diodes have been developed using III—Nitride and II–VI strained layers. Improved mid-infrared lasers, using Sb-based III–V semiconductor strained layers, have also been fabricated. These advances have been possible due to improvements in growth techniques as well as in the modelling and computer simulations of layers compositions and device structures. Full band Monte Carlo simulations of electron transport in strained Si predict very high electron mobilities. Computer simulations show that complementary metal oxide silicon circuits, fabricated with strained layer GeSi transistors will have considerably improved performance. Electronic devices based on GeSi strained layers have shown further improvements in high frequency and high power performance. Many devices based on strained layers are being used in commercial equipment. Advances have been made both in modelling and determining the nonuniform strain, using a Raman technique.     

Downward two-phase flow applications for a non-conventional heat pump

A non-conventional heat pump working by a difference in density between two branches of a hydraulic vertical loop has been described. This system called thermogravimetric heat pump, TGHP, operates with a non-conventional regenerative thermodynamic cycle which remarkably improves COP values. The lower density in the ‘downward branch’ is obtained by a liquid–vapour two-phase flow. Performances and main geometrical characteristic trends, such as plant height Z and two-phase column diameter D_T–PD have been drawn, varying the minimum cycle temperature between 15 and 25 °C and the user temperature, T_max, in the range 60–70 °C. The carrier fluid is demineralized water; according to the peculiar working fluid—PP 50, HFC 134a and HFC 338cca—different solutions can be obtained, such as for 10–12 storey buildings or for skyscrapers. Yet, the results obtained with HFC 338cca must be accepted with some cautions while waiting for a better characterisation of such fluid. Chemical compatibility, thermal stability, environmental impact have been also taken into account in the choice of the operating couple, carrier fluid—working fluid. While the thermodynamic conversion process is non-conventional, the TGHP can be assembled by standardised technology. The compressor of a conventional plant is here replaced by a feeding pump and COP values obtained through a regenerative TGHP are globally larger than those of a common heat pump.     

Magnetic field hysteresis of critical currents in Bi(2223)/Ag tapes and a way to overcome it

Experiments showing hysteresis of critical currents versus the external magnetic field I_c(B_e) were performed with two multifilamentary Bi(2223)/Ag tapes. The I_c(B_e) hysteresis is observable in the transversal as well as in the longitudinal orientation of the long axis of the tape with respect to the magnetic field. Based on the idea that the hysteresis is the effect of trapped flux in a network of well-connected current paths, a way to overcome this effect has been proposed and experimentally verified. The induced frozen-in screening currents are split into several parallel current patterns by cycling the external magnetic field around the adjusted value. Using the proposed method, the ‘neutral’ I_c(B_e) characteristics have been found. Approximate calculations of the penetration depth of the trapped flux show that the network of well-connected current paths could be formed by several disk-shaped grains (≈ Φ8 × 0.4 μ) stacked into more or less axially ordered (quasi cylindrical) colonies of average dimensions estimated to ≈ Φ8 × 4 μm.     

A study of phase separation in ternary alloys

We have studied the evolution of microstructure when a disordered ternary alloy is quenched into a ternary miscibility gap. We have used computer simulations based on multicomponent Cahn-Hilliard (CH) equations for c _A and c_B, the compositions (in mole fraction) of A and B, respectively. In this work, we present our results on the effect of relative interfacial energies on the temporal evolution of morphologies during spinodal phase separation of an alloy with average composition, c_A = 1/4, c_B = 1/4 and c_c = 1/2. Interfacial energies between the ‘A’ rich, ‘B’ rich and ‘C’ rich phases are varied by changing the gradient energy coefficients. The phases associated with a higher interfacial energy are found to be more rounded than those with lower energy. Further, the kinetic paths (i.e. the history of A-rich, B-rich and C-rich regions in the microstructure) are also affected significantly by the relative interfacial energies of the three phases.     

Deformation mechanisms, electronic conductance and friction of metallic nanocontacts.

Close interactions between experiments and computer simulations of metallic contacts have revealed the central role of mechanical instabilities in the evolution of the electronic conductance of atomic-scale contacts pulled to fracture. At the same time crucial differences in the time scales of relaxation processes that occur in experiments and in simulations have been highlighted and have raised fundamental questions about modelling strategies.     

‘Electromaglev’-magnetic levitation of a superconducting disc with a DC field generated by electromagnets: Part 1. Theoretical and experimental results on operating modes, lift-to-weight ratio, and suspension stiffness

We present results of a comprehensive study, both theoretical and experimental, of an ‘electromaglev’ system, in which a high-temperature superconducting bulk sample, e.g. YBa₂Cu₃O_7−δ (YBCO), is levitated stably in a DC magnetic field generated by electromagnets placed underneath the floating object. Results of the zeroth-order theory agree quite well with experimental results on lift-to-weight ratio and suspension stiffness for three bulk samples: (1) a solid YBCO disc; (2) a YBCO annulus; and (3) a YBCO annulus with a neodymium-iron-boron (Nd-Fe-B) permanent magnet disc (PMD) filling the centre. The experiment has also verified the need to satisfy two requirements to achieve stable levitation with a DC magnetic field only: (1) the spatial flow of the supercurrent in the sample must have at least two degrees of freedom; and (2) the electromagnets must generate a magnetic field profile that satisfies spatial requirements for lateral and pitch stability. A permanent magnet disc has only one degree of freedom for its Amperian current, thus it cannot be levitated stably in this system; the experiment has also demonstrated that an HTS solenoid (wound with silver-sheathed BSCCO-2223 tape) cannot be levitated stably, because the solenoid supercurrent flow is also restricted to the azimuthal direction only. The zeroth-order theory together with the Bean model shows that the supercurrent induced in a YBCO sample is independent of the critical current density, J_c, of the material but is directly proportional to the axial component of the field and that the lift of the sample is directly proportional to the product of the axial and radial components of the magnetic field generated by the electromagnets.     

Linear scaling methods for electronic structure calculations and quantum molecular dynamics simulations

In the past five years, notable advances in the field of electronic structure calculations have been made, by the development of linear scaling methods for total energy calculations and quantum molecular dynamics simulations. These are methods implying a computational workload which grows linearly with th system-size,in contrast to standard algorithms where the workload scales as the cube of the system-size. Therefore the use of linear scaling methods can considerably widen the class of systems and type of problems being tackled with quantum simulations. At present, linear scaling methods using semi-empirical Hamiltonians allow one to perform simulations involving up to a thousand atoms on small workstations, and up to ten thousand atoms for tens of picoseconds when using supercomputers. This has made it possible to study problems such as large organic molecules in water, thin film growth on a surface and extended defects in semiconductors. Although the implementation of first-principles linear scaling methods is less advanced than that of semi-empirical methods, promising results regarding organic molecules and metal-alloys have already appeared in the literature.     

Application of genetic algorithms to hydrogenated silicon clusters

We discuss the application of biologically inspired genetic algorithms to determine the ground state structures of a number of Si-H clusters. The total energy of a given configuration of a cluster has been obtained by using a non-orthogonal tight-binding model and the energy minimization has been carried out by using genetic algorithms and their recent variant differential evolution. Our results for ground state structures and cohesive energies for Si-H clusters are in good agreement with the earlier work conducted using the simulated annealing technique. We find that the results obtained by genetic algorithms turn out to be comparable and often better than the results obtained by the simulated annealing technique.     

An experimental study on HC290 and a commercial liquefied petroleum gas (LPG) mix as suitable replacements for HCFC22

This paper presents an experimental study on the performance of hydrocarbon refrigerants, namely propane and a liquefied petroleum gas (LPG) mix as suitable replacements for the widely used refrigerant HCFC22 in refrigeration and heat pump applications. A cylinder of commercially available LPG from New Zealand market was obtained for this study. The composition of the specific LPG mix (by mass fraction) was propane (HC290)—98.95%, ethane (HC170)—1.007%, iso-butane (HC600a)—0.0397% and other constituents in small proportions. Experiments were carried out in a laboratory heat pump test facility with maximum condenser capacity of approximately 15 kW. Condensing temperatures were held constant at 35, 45 and 55°C, while evaporating temperatures were varied over a wide range from − 15 to + 15°C. All tests were carried out at constant degree of superheat (about 1 K) and subcooling (about 8 K). All appropriate precautions were observed against any leaks or fire.The analysis revealed that the hydrocarbon refrigerants performed better than HCFC22 but with a small loss of condenser capacity. The mass flow rate and compressor discharge temperature were found to be significantly lower than HCFC22. The performance of the specific LPG mix tested was found to be better than HC290 at higher condensing temperatures but poorer at a lower condensing temperature. No adverse effects were found with the LPG mix despite the presence of little moisture (less than 0.01%) in its composition. The study reveals that LPG of the tested composition (i.e. predominantly a mixture of propane, ethane and iso-butane) can be an excellent refrigerant in heat pump/refrigeration applications.     

Heat transfer through subcooled He I layer from distributed heat source in a pressurized He II channel

The subcooled He I layer, in contact with a large heated surface in a channel filled with the pressurized superfluid He II (He II_p), expands the non-boiling region above the Kapitza region up to q_n, above which nucleate boiling sets in. As the bath temperature decreases, q_n is increased more rapidly than q_λ at which the superfluidity is broken at the centre of the heated surface. The value of q_n is increased as the channel gap increases, and is independent of the channel orientation as well as q_λ. Metastabilization of superconducting coils may be enhanced by taking the non-boiling limit q_n into account.     

Application of mass spectrometry to the characterization of polymers

Recent advances in soft ionization techniques for mass spectrometry of polymeric materials make it possible to determine the mass of intact molecular ions exceeding 1 × 10⁶ Da. Developments in high resolution mass spectrometers have additionally led to impressive advances in our ability to characterize polymers. The entire molecular mass distribution of a polymer sample can be accurately measured. From the molecular mass, the molecular formulae and information regarding polymer composition and end-groups can be deduced. The two techniques which have received the most attention are matrix-assisted laser desorption/ionization and electrospray ionization. In recent work, these techniques have been combined with chromatographic separations, and a series of mass spectra are acquired for each fraction of the distribution. This simplifies the analysis by reducing the number of components present in each mass spectrum, and additionally improves quantitation.     

Mathematical modeling of scroll compressors — part II: overall scroll compressor modeling

This paper presents the development of a comprehensive simulation model of a horizontal scroll compressor, which combines a detailed compression process model (Chen Y., Halm N., Groll E., Braun J. Mathematical modelling of scroll compressors — part I: compression process modeling, International Journal of Refrigeration 2002;25(6):731–750) and an overall compressor model. In the overall model, compressor components are analyzed in terms of nine different elements. Steady state energy balance equations are established applying the lumped capacitance method. In combination with the detailed compression process model, these equations were implemented into computer code and solved recursively. In this way, the temperature and pressure of the refrigerant in different compressor chambers, the temperature distributions in the scroll wraps, and the temperatures of the other compressor elements can be obtained. Thereafter, power consumption and efficiency of the compressor can be calculated. Tests were used to verify the overall model on a macroscopic basis. Using the simulation program based on the overall compressor model, a parametric study of the scroll compressor was performed, and the effects of internal leakage and heat transfer losses were investigated and some preliminary results were obtained. These results indicate that the comprehensive scroll compressor model is capable of predicting real compressor behavior and useful to the design and optimization of scroll compressors.     

Novel caged clusters of silicon: Fullerenes,Frank-Kasper polyhedron and cubic

We review recent findings of metal (M) encapsulated caged clusters of Si and Ge obtained from computer experiments based on an ab initio pseudopotential method. It is shown that one M atom changes drastically the properties of Si and Ge clusters and that depending upon the size of the M atom, cages of 14, 15, and 16 Si as well as Ge atoms are formed. In particular M@Si₁₆ silicon fullerene has been obtained for M= Zr and Hf, while a Frank-Kasper polyhedron has been obtained for M@X₁₆, X = Si and Ge. These clusters show high stability and large highest occupied-lowest unoccupied molecular orbital (HOMO-LUMO) gaps which are likely to make these species strongly abundant. A regular icosahedral M@X₁₂ cluster has also been obtained for X = Ge and Sn by doping a divalent M atom. Interactions between clusters are rather weak. This is attractive for developing self-assembled cluster materials.     

Structural Studies of the Superconducting La2.5Y0.5CaBa3(Cu1?xFex)7Oz (0 ≤ x ≤ 0.1) Perovskite System by Neutron Diffraction

We have investigated the effect of Fe substitution on the structural and superconducting properties of La_2.5Y_0.5CaBa₃(Cu_1–x Fe _x )₇O _z system by Rietveld refinement of the neutron diffraction patterns of three samples with x = 0.02 (labelled B₁), x = 0.06 (B₂), and x = 0.10 (B₃) along with X-ray diffraction, resistivity, AC susceptibility, and oxygen-content measurements. Samples B₁, B₂, and B₃ are superconducting with T _c ^R=0 values of 73, 62, and 41 K, respectively. Neutron diffraction studies confirm (i) the formation of a single phase tetragonal structure (space group P4/mmm) for all three samples, (ii) Ca and Y ions substitution at the La site concomitantly displaces La onto Ba sites, and (iii) increasing x from 0.02 to 0.10 increases oxygen content (the amount of oxygen per unit cell), as well as Cu(1)— O(4) and Cu(1)— O(1) bond lengths whereas Cu(2)— O(4) bond length decreases with corresponding decrease in T _c to 41 K due to increasing occupancy of Fe ions at Cu(2) site. The change in bond lengths with oxygen content are essentially the same as those of Fe content (x). Present studies establish a correlation between the bond lengths (Cu(1)— O(1), Cu(1)— O(4), and Cu(2)— O(4)) and the measured T _c values of three samples.