Standardization of Methods for Characterizing the Surface Geometry of Solids

Since a comprehensive survey published in 1999 [1] much work was done in standardizing measuring methods to characterize the surface geometry of dispersed and/or porous solids and to certify reference materials. The present paper is an extension of a short communication [2]. It gives a survey on existing standards and reports on new drafts and proposals.     

Pressure-temperature phase diagrams of smectogenic 4'-alkyl-4-cyanobiphenyls (9CB, 10CB, 11CB and 12CB)

The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members.     

Extension of the measuring range of balances

The basic principle of comparing the sample mass with the mass of a reference body in equilibrium gives the equal-armed beam balance a unique accuracy. Main parameters characterising the suitability of the instrument are measuring range, resolution and relative sensitivity (resolution/maximum load). The historical development of the values of these parameters achieved depended strongly on the practical need in those times. Technically unfavourable scales of the oldest Egyptian dynasties (~3000 BC) could resolve mass differences of 1 g and had a relative sensitivity of at least 10^–3. More sophisticated instruments from the 18^th Dynasty (~1567–1320 BC) achieved a relative sensitivity of 10^–4 independent of the size of the instrument. In 350 BC Aristotle clarified the theory of the lever and at about 250 BC Archimedes used the balance for density determinations of solids. The masterpiece of a hydrological balance was Al Chazini’s 'Balance of Wisdom’ built about 1120. Its relative sensitivity was 2⋅10^–5. Real progress took place when scientists like Lavoisier (1743–1794) founded modern chemistry. At the end of the 19^th century metrological balances reached a relative sensitivity of 10^–9 with a maximum load of several kilogrammes. That seems to be the high end of sensitivity of the classical mechanical beam balance with knife edges. Improvements took place by electrodynamic compensation (Emich, Gast). In 1909 Ehrenhaft and Millikan could weigh particles of 10^–15 g by means of electrostatic suspension. In 1957 Sauerbrey invented the oscillating quartz crystal balance. By observing the frequency shift of oscillating carbon nanotubes or of silica nanorods, masses or mass changes in the attogram or zeptogram have been observed recently.     

Comments on surface structure analysis by water and nitrogen adsorption

Specific surface area and pore size distribution are determined usually from adsorption isotherms at low temperatures using nitrogen or noble gases. These are not absolute parameters and the measuring methods are fraught with serious difficulties. General problems of sorption measurements and recent developments are discussed. To obtain information for practical purposes these measurements need to be supplemented by investigations of the sorbate/sorbent system used in practice. Results of the measurement of nitrogen and water vapour adsorption on different materials are compared. This revised version was published online in July 2006 with corrections to the Cover Date.     

Steam-carbon gasification catalyzed by calcium: Assessment of the porous structure of active carbons from plum stones and synthetic active carbons

A need for an elaboration of the methods for synthesis and characterization of activated carbons with a requisite porous structure has existed for a long time. One of the methods giving possibility for creating controlled mesopore and micropore structures deals with the steam gasification of various carbon materials. In this work the effects of calcium catalyst on the catalytic steam gasification of active carbons from plum stones and porous polymers are presented. Determination of micropores capacity and specific adsorption in mesopores have been performed by means of the _s method, but adsorption on the heterogeneous solids was described by the integral equation with various local isotherms. This equation has been solved by the regularization method. Based on this method the changes in structural parameters of active carbons depending on the amount of calcium catalyst were estimated.Nomenclature d width of slit-like micropore - F(x) distribution function of the half-width - p vapor pressure of sorbate - p/p _N relative pressure - PSAC Plum Stone Active Carbon - average pore radius, nm - S ₁ relative limit of the validity of experimental point on the adsorption isotherm in the computations by means of regularization method - SAC Synthetic Active Carbon - S _BET specific surface area calculated by means of BET method, m²/g - S _mes mesopore surface area, m²/g - S _mic micropore surface area, m²/g - T absolute temperature, K - V _mes sorption capacity of mesopores, cm³/g - V _mic sorption capacity of micropores, cm³/g - V _p sorption capacity of pores, cm³/g - w/w weight in weight concentration - x half-width of slit-like micropore, nm - x ₁ maximum of half-width of micropore slit, nm - average half-width of slit-like micropore, nm - X _min-X _max integration limits of thex Greek Letters Greek Letters variance of average half-width of slit-like micropore, nm² - local relative filling of micropores - total relative filling of micropores     

A study on the metalation of alkoxydibromobenzenes

The metalation of (quasi)alkoxy-substituted dibromobenzenes C₆H₃(OR)Br₂ with lithium diisopropylamide (LDA) has been investigated. For 1-(quasi)alkoxy-3,5-dibromobenzenes (R = Me, TMS), different selectivities were observed depending on reaction conditions and the size of the alkoxy group. The methoxy group was an effective ortho-director whereas this was not the case for the bulky trimethylsilyloxy group. The metalation of related 2,5-dibromoanisole was also examined showing a significant meta-directing effect by the methoxy group. The thermal stability of aryllithium intermediates is significantly lower when lithium is flanked by a bromine and a methoxy group, whereas 4-(quasi)alkoxy-2,6-dibromoaryllithiums are less labile.     

Comparative electrooptic study of new orthoconic liquid crystals with fluorinated alkoxy terminal chains

Electrooptical properties of several new orthoconic antiferroelectric liquid crystal mixtures with partially fluorinated alkoxyalkoxy terminal chains have been investigated in order to select the best mixture for display applications. Electrooptical studies have been performed on these orthoconic materials aiming at evaluating their static and dynamic performance under passive multiplexing conditions. A number of parameters have been evaluated, static and dynamic contrast, driving scheme for passive multiplexing, rise and fall response times, dynamic range, and dynamic greyscale.     

New liquid-crystalline isothiocyanates with high clearing points,low viscosities and strong nematic character

Abstract

Bi-, tri- and tetra-ring liquid-crystalline compounds with an isothiocyanate group in the terminal position of the molecule and with an ethylene group in the central position have been synthesized. Phenyl, cyclohexyl, bicyclo[2,2,2]octyl, 1,3-dioxane and pyrimidinyl were used as the ring systems. Their transition temperatures and melting enthalpies have been determined. The relationship between the order of the rings in the molecule and the clearing points and melting points of the compounds is discussed. It is shown that these compounds are valuable components of liquid crystal mixtures, since they effectively raise their clearing points yet only have a small effect on the viscosity.     

Fast polarisation-insensitive optical shutter supported by backflow in dichroic dye-doped dual-frequency liquid crystal

This paper describes a novel implementation of a dual-frequency liquid crystal optical shutter of the guest–host type. The transmissive state of the filter is obtained by applying a low-frequency electric field that brings the dichroic dye in a homeotropic orientation. The light-absorbing state is realised by a twisted planar configuration for which the absorption is quasi-independent of the polarisation. Switching between the two states occurs in about 1 ms and the devices show no scattering for wavelengths inside or outside the absorption band of the dichroic dye. Simulations and experiments reveal how a twisted state is obtained through the backflow phenomenon.     

Dielectric studies of two liquid crystalline benzoates with coupled and decoupled CN groups

The results of dielectric studies performed in a broad frequency range for two compounds, 4-cyanophenyl 4-n-heptylbenzoate (7BBCN) and 4-(4-cyanobutyloxy)phenyl 4- n-heptylbenzoate (7BB4CN), are compared. They have the same molecular core whereas the strongly polar CN group is attached to the benzene ring in 7BBCN or is separated from it by the butyloxy chain in 7BB4CN. 7BBCN has a nematic phase, whereas 7BB4CN exhibits a monotropic nematic and smectic A₂ polymorphism. Large differences in the dielectric properties of the two substances were found. The analysis of the results led to the conclusion that the antiparallel dipole-dipole associations are considerably stronger in the substance with a decoupled CN group.