Electro-optical properties of liquid crystal copolymers and their relationship to structural order

A range of side chain liquid crystal copolymers have been prepared using mesogenic and non-mesogenic units. It is found that high levels of the non-mesogenic moieties may be introduced without completely disrupting the organization of the liquid crystal phase. Incorporation of this comonomer causes a marked reduction in the glass transition temperature (Tg), presumably as a result of enhanced backbone mobility and a corresponding lowering of the nematic transition temperature, thereby restricting the temperature range for stability of the liquid crystal phase. The effect of the interactions between the various components of these side-chain polymers on their electro-optic responses is described. Infrared (i.r.) dichroism measurements have been made to determine the order parameters of the liquid crystalline side-chain polymers. By identifying a certain band (CN stretching) in the i.r. absorption spectrum, the order parameter of the mesogenic groups can be obtained. The temperature and composition dependence of the observed order parameter are related to the liquid crystal phase transitions and to the electro-optic response. It is found that the introduction of the non-mesogenic units into the polymer chain lowers the threshold voltage of the electro-optic response over and above that due to the reduction in the order parameter. The dynamic electro-optic responses are dominated by the temperature-dependent viscosity and evidence is presented for relaxation processes involving the polymer backbone which are on a time scale greater than that for the mesogenic side-chain units.

Temperature-tuned vector phase conjugation in azobenzene dye impregnated polymer films

Near-perfect vector phase conjugation was achieved at 488 nm in a methyl red dye impregnated polymethylmethacrylate film by employing a temperature tuning technique. Using a degenerate four-wave mixing geometry with vertically polarized counterpropagating pump beams, intensity and polarization gratings were written in the dye/polymer system using a vertically or horizontally polarized weak probe beam. Over a limited temperature range, as the sample was heated, the probe reflectivity from the polarization grating dropped but the reflectivity from the intensity grating rose sharply. At a sample temperature of approximately 50°C, the reflectivities of the gratings were measured to be equal and we confirmed that, at this temperature, the measured vector phase conjugate fidelity was very close to unity. We discuss a possible explanation of this effect.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Cooperative metal-ligand-induced properties of heteroleptic copper(I) xanthate/dithiocarbamate PPh3 complexes

Four new heteroleptic mononuclear complexes, [Cu(PPh3)2L1](1) {L1 = (C9H11O2CS2), [2-(4-methoxyphenyl)ethyl]xanthate}, [Cu(PPh3)2L2] (2) [L2 = (C6H7OCS2), benzylxanthate], [Cu(PPh3)2L3] (3) [L3 = (C5H9OCS2), (cyclobutylmethyl)xanthate] and [Cu(PPh3)2L4] (4) [L4 = (NC13H13NCS2), N-benzyl-N-(4-pyridylmethyl)dithiocarbamate], have been synthesized and characterized by using microanalysis, IR, UV/Vis, 1H, 13C and 31P NMR spectroscopy and X-ray crystallography; their photoluminescent behaviour and molecular electrical conductivity have been investigated. CuI possesses four-coordinate distorted tetrahedral geometry in all the complexes. All are weakly conducting and exhibit semiconductor behaviour in the studied 303363 K temperature range. Complex 4 shows striking luminescent behaviour emitting bluish green light at 480 nm in CH2Cl2 solution at room temperature

Structure and magnetic properties of a tetranuclear Cu(II) complex containing the 2-(pyridine-2-yliminomethyl)-phenol ligand

A tetranuclear Cu(II) complex [Cu4L4(H2O)4](ClO4)4 has been synthesized using the terdentate Schiff base 2-(pyridine-2-yliminomethyl)-phenol (HL) (the condensation product of salicylaldehyde and 2-aminopyridine) and copper perchlorate. Chemical characterizations such as IR and UV/Vis of the complex have been carried out. A single-crystal diffraction study shows that the complex contains a nearly planar tetranuclear core containing four copper atoms, which occupy four equivalent five-coordinate sites with a square pyramidal environment. Magnetic measurements have been carried out over the temperature range 2–300K and with 100Oe field strengths. Analysis of magnetic susceptibility data indicates a strong antiferromagnetic (J1=−638cm−1) exchange interaction between diphenoxo-bridged Cu(II) centers and a moderate antiferromagnetic (J2=−34cm−1) interaction between N–C–N bridged Cu(II) centers. Magnetic exchange interactions (J’s) are also discussed on the basis of a computational study using DFT methodology. The spin density distribution (singlet ground state) is calculated to visualize the effect of delocalization of spin density through bridging groups.

Measurements of NO, NOy, N2O, and O3 during SPURT: implications for transport and chemistry in the lowermost stratosphere

We present measurements of NO, NOy, O3, and N2O within the lowermost stratosphere (LMS) over Europe obtained during the SPURT project. The measurements cover all seasons between November 2001 and July 2003. They span a broad band of latitudes from 30° N to 75° N and a potential temperature range from 290 to 380 K. The measurements represent a comprehensive data set of these tracers and reveal atmospheric transport processes that influence tracer distributions in the LMS. Median mixing ratios of stratospheric tracers in equivalent latitude-potential temperature coordinates show a clear seasonal cycle related to the Brewer-Dobson circulation, with highest values in spring and lowest values in autumn. Vertical tracer profiles show strong gradients at the extratropical tropopause, suggesting that vertical (cross-isentropic) mixing is reduced above the tropopause. Pronounced meridional gradients in the tracer mixing ratios are found on potential temperature surfaces in the LMS. This suggests strongly reduced mixing along isentropes. Concurrent large gradients in static stability in the vertical direction, and of PV in the meridional direction, suggest the presence of a mixing barrier. Seasonal cycles were found in the correlation slopes ΔO3/ΔN2O and ΔNOy/ΔN2O well above the tropopause. Absolute slope values are smallest in spring indicating chemically aged stratospheric air originating from high altitudes and latitudes. Larger values were measured in summer and autumn suggesting that a substantial fraction of air takes a "short-cut" from the tropical tropopause region into the extratropical LMS. The seasonal change in the composition of the LMS has direct implications for the ozone chemistry in this region. Comparisons of measured NO with the critical NO value at which net ozone production changes from negative to positive, imply ozone production up to 20 K above the local tropopause in spring, up to 30 K in summer, and up to 40 K in autumn. Above these heights, and in winter, net ozone production is negative.

A self-calibrating electrometer for atmospheric charge measurements from a balloon platform

Charged aerosol particles and water droplets are abundant throughout the lower atmosphere, and may influence interactions between small cloud droplets. This note describes a small, disposable sensor for the measurement of charge in non-thunderstorm cloud, which is an improvement of an earlier sensor [K. A. Nicoll and R. G. Harrison, Rev. Sci. Instrum. 80, 014501 (2009)]. The sensor utilizes a self-calibrating current measurement method. It is designed for use on a free balloon platform alongside a standard meteorological radiosonde, measuring currents from 2 fA to 15 pA and is stable to within 5 fA over a temperature range of 5 °C to −60 °C. During a balloon flight with the charge sensor through a stratocumulus cloud, charge layers up to 40 pC m−3 were detected on the cloud edges.

Synthesis, structural characterisation and thermoelectric properties of Bi1−xPbxOCuSe

The effect of Pb2+ doping on the structure and thermoelectric properties of BiOCuSe (also known as BiCuSeO or BiCuOSe) is described. With increasing Pb2+ content, the expansion of the unit cell results in a weakening of the bonding between the [Bi2(1-x) Pb2xO2]2(1-x)+ and the [Cu2Se2]2(1-x)- layers. The electrical resistivity and Seebeck coefficient decrease in a systematic way with growing Pb2+ levels. The thermal conductivity rises due to the increase of the electronic contribution with doping. The power factor of materials with a 4-5% Pb2+ content takes values of ca. 8 W cm-1 K-2 over a wide temperature range. ZT at 673 K is enhanced by ca. 50% when compared to values found for other dopants, such as Sr2+ or Mg2+.

Temperature trends at the Mauna Loa observatory, Hawaii

Observations at the Mauna Loa Observatory, Hawaii, established the systematic increase of anthropogenic CO2 in the atmosphere. For the same reasons that this site provides excellent globally averaged CO2 data, it may provide temperature data with global significance. Here, we examine hourly temperature records, averaged annually for 1977–2006, to determine linear trends as a function of time of day. For night-time data (22:00 to 06:00 LST (local standard time)) there is a near-uniform warming of 0.040 °C yr−1. During the day, the linear trend shows a slight cooling of −0.014 °C yr−1 at 12:00 LST (noon). Overall, at Mauna Loa Observatory, there is a mean warming trend of 0.021 °C yr−1. The dominance of night-time warming results in a relatively large annual decrease in the diurnal temperature range (DTR) of −0.050 °C yr−1 over the period 1977–2006. These trends are consistent with the observed increases in the concentrations of CO2 and its role as a greenhouse gas (demonstrated here by first-order radiative forcing calculations), and indicate the possible relevance of the Mauna Loa temperature measurements to global warming.

Climate at high-obliquity

The question of climate at high obliquity is raised in the context of both exoplanet studies (e.g. habitability) and paleoclimates studies (evidence for low-latitude glaciation during the Neoproterozoic and the ”Snowball Earth” hypothesis). States of high obliquity, φ, are distinctive in that, for φ ≥54◦, the poles receive more solar radiation in the annual mean than the Equator, opposite to the present day situation. In addition, the seasonal cycle of insolation is extreme, with the poles alternatively “facing” the sun and sheltering in the dark for months. The novelty of our approach is to consider the role of a dynamical ocean in controlling the surface climate at high obliquity, which in turn requires understanding of the surface winds patterns when temperature gradients are reversed. To address these questions, a coupled ocean-atmosphere-sea ice GCM configured on an aquaplanet is employed. Except for the absence of topography and modified obliquity, the set-up is Earth-like. Two large obliquities φ, 54◦ and 90◦, are compared to today’s Earth value, φ=23.5◦. Three key results emerge at high obliquity: 1) despite reversed temper- ature gradients, mid-latitudes surface winds are westerly and trade winds exist at the equator (as for φ=23.5◦) although the westerlies are confined to the summer hemisphere, 2) a habitable planet is possible with mid-latitude temperatures in the range 300-280 K and 3) a stable climate state with an ice cap limited to the equatorial region is unlikely. We clarify the dynamics behind these features (notably by an analysis of the potential vorticity structure and conditions for baroclinic instability of the atmosphere). Interestingly, we find that the absence of a stable partially glaciated state is critically linked to the absence of ocean heat transport during winter, a feature ultimately traced back to the high seasonality of baroclinic instability conditions in the atmosphere.

Rheological and electrical properties of NaY zeolite electrorheological fluid

The relations between the rheological and electrical properties of NaY zeolite electrorheological fluid and its solid phase are studied. It is found that then exist complex relations between its electrical and theological properties. The temperature spectra of dielectric properties of the fluid under high AC electric field are strongly field strength dependent. The relation between the DC conductivity of the fluid and the exciting electric field is experimentally presented as log sigma =A+BE1/2, when A is a strong function, but B, a very weak function of temperature. The shear stress of the fluid under a fixed electric field and temperature decreases with shear rate. A relaxation time for the adsorbed charges is estimated to be about 0.3 to 6.6 s in the temperature range from 280 to 380 K. The relaxation time qualitatively corresponds to the shear rate at which the shear stress begins to drop. The time dependent leaking current of the ER fluids under DC electric field is also measured. The conductivity increase is mainly caused by the structure evolution of particles. The experimental results can he explained with the calculations of Davis (J. Appl. Phys. 81(1997) pp.1985-1991) and Martin (J. Chem. Phys. 110(1999) pp.4854-4866). It is predicted that the NaY zeolite ER fluid strength would get degraded slowly.

Fabrication and evaluation of a skutterudite-based thermoelectric module for high-temperature applications

We report a straightforward methodology for the fabrication of high-temperature thermoelectric (TE) modules using commercially available solder alloys and metal barriers. This methodology employs standard and accessible facilities that are simple to implement in any laboratory. A TE module formed by nine n-type Yb x Co4Sb12 and p-type Ce x Fe3CoSb12 state-of-the-art skutterudite material couples was fabricated. The physical properties of the synthesized skutterudites were determined, and the module power output, internal resistance, and thermocycling stability were evaluated in air. At a temperature difference of 365 K, the module provides more than 1.5 W cm−3 volume power density. However, thermocycling showed an increase of the internal module resistance and degradation in performance with the number of cycles when the device is operated at a hot-side temperature higher than 573 K. This may be attributed to oxidation of the skutterudite thermoelements.

Understanding the rapid summer warming and changes in temperature extremes since the mid-1990s over Western Europe

Analysis of observations indicates that there was a rapid increase in summer (June-August, JJA) mean surface air temperature (SAT) since the mid-1990s over Western Europe. Accompanying this rapid warming are significant increases in summer mean daily maximum temperature, daily minimum temperature, annual hottest day temperature and warmest night temperature, and an increase in frequency of summer days and tropical nights, while the change in the diurnal temperature range (DTR) is small. This study focuses on understanding causes of the rapid summer warming and associated temperature extreme changes. A set of experiments using the atmospheric component of the state-of-the-art HadGEM3 global climate model have been carried out to quantify relative roles of changes in sea surface temperature (SST)/sea ice extent (SIE), anthropogenic greenhouse gases (GHGs), and anthropogenic aerosols (AAer). Results indicate that the model forced by changes in all forcings reproduces many of the observed changes since the mid-1990s over Western Europe. Changes in SST/SIE explain 62.2% ± 13.0% of the area averaged seasonal mean warming signal over Western Europe, with the remaining 37.8% ± 13.6% of the warming explained by the direct impact of changes in GHGs and AAer. Results further indicate that the direct impact of the reduction of AAer precursor emissions over Europe, mainly through aerosol-radiation interaction with additional contributions from aerosol-cloud interaction and coupled atmosphere-land surface feedbacks, is a key factor for increases in annual hottest day temperature and in frequency of summer days. It explains 45.5% ± 17.6% and 40.9% ± 18.4% of area averaged signals for these temperature extremes. The direct impact of the reduction of AAer precursor emissions over Europe acts to increase DTR locally, but the change in DTR is countered by the direct impact of GHGs forcing. In the next few decades, greenhouse gas concentrations will continue to rise and AAer precursor emissions over Europe and North America will continue to decline. Our results suggest that the changes in summer seasonal mean SAT and temperature extremes over Western Europe since the mid-1990s are most likely to be sustained or amplified in the near term, unless other factors intervene.

Study of the pozzolanic reaction kinetics in sugar cane bagasse-clay ash/calcium hydroxide system: kinetic parameters and pozzolanic activity

This paper presents a study of the pozzolanic reaction kinetics between calcium hydroxide and a mixture of sugar cane bagasse with 20 and 30% of clay, burned at 800 and 1000 degrees C (SCBCA) by electrical conductivity measurements. A kinetic-diffusive model produced in previous studies by some of the authors was used. The model was fitted to the experimental data, which allowed the computation of the kinetic parameters of the pozzolanic reaction (reaction rate constant and free energy of activation) that rigorously characterised the pozzolanic activity of the materials. The results show that SCBCA demonstrated reactivity and good pozzolanic qualities in the range 800-1000 degrees C.

Interparticle Interactions Effects on the Magnetic Order in Surface of Fe(3)O(4) Nanoparticles

We report interparticle interactions effects on the magnetic structure of the surface region in Fe(3)O(4) nanoparticles. For that, we have studied a desirable system composed by Fe(3)O(4) nanoparticles with (d) = 9.3 nm and a narrow size distribution. These particles present an interesting morphology constituted by a crystalline core and a broad (similar to 50% vol.) disordered superficial shell. Two samples were prepared with distinct concentrations of the particles: weakly-interacting particles dispersed in a polymer and strongly-dipolar-interacting particles in a powder sample. M(H, T) measurements clearly show that strong dipolar interparticle interaction modifies the magnetic structure of the structurally disordered superficial shell. Consequently, we have observed drastically distinct thermal behaviours of magnetization and susceptibility comparing weakly- and strongly-interacting samples for the temperature range 2 K < T < 300 K. We have also observed a temperature-field dependence of the hysteresis loops of the dispersed sample that is not observed in the hysteresis loops of the powder one.