Rigid tetracatenar liquid crystals derived from 1,10-phenanthroline

Tetracatenar liquid crystals were obtained by substituting the 1,10-phenanthroline central core unit at the 3- and 8-positions by extended, rigid acetylene moieties, equipped at the termini with two alkoxy chains of various lengths (n = 6, 8, 10, 12, 14). The liquid crystals exhibit a rich mesomorphism including smectic C, cubic, hexagonal and rectangular columnar phases, depending on the alkoxy chain length. The corresponding rhenium(I) complexes containing the bulky [ReBr(CO)₃] fragment are not liquid-crystalline. The ligands and rhenium(I) complexes were investigated by scanning tunneling microscopy (STM). Both the ligands and the rhenium(I) complexes can be self-assembled into monolayers at the TCB–graphite and octanoic acid–graphite interfaces. The ligands and rhenium(I) complexes are luminescent.

Pyrrolidinium Ionic Liquid Crystals

N-Alkyl-N-methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)-imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2-thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl] counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group CnH2n+1 was varied from eight to twenty carbon atoms (n =8. 10-20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal. columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the Molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X-ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self-assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium-containing mesogens, luminescence can be induced by dissolving them in an ionic: liquid matrix. The europium-containing compound shows intense red photoluminescence with high colour Purity.

Pyrrolidinium Ionic Liquid Crystals with Pendant Mesogenic Groups

New ionic liquid crystals (including ionic metallomesogens) based oil the pyrrolidinium core are presented. N-Methylpyrrolidine was quaternized with different mesogenic groups connected to a flexible, omega-bromosubstituted alkyl spacer. The length of the flexible alkyl spacer between the cationic head group and the rigid mesogenic group was varied. The substituted pyrrolidinium cations were combined with bromide, bis(trifluoromethylsulfonyl)imide, tetrakis (2-thenoyltrifluoroacetonato)europate(III), and tetrabromouranyl anions. The influence of the type of mesogenic unit, the lengths of the flexible spacer and terminal alkyl chain, the size of the mesogenic group, and the type of anion oil the thermotropic mesomorphic behavior was investigated. Furthermore, the phase behavior was thoroughly compared with the previously reported mesomorphism of N-alkyl-N-methylpyrrolidinium salts. Low-ordered smectic A phases of the de Vries type, smectic C phases, higher-ordered smectic F/I phases, as well its crystal smectic phases (E and G, J, H, or K) were observed and investigated by polarizing optical microscopy, differential scanning calorimetry, and powder X-ray diffraction.

Filling Ability and Plastic Settlement of Self-Compacting Concrete

The use of self-compacting concrete (SCC) facilitates the placing of concrete by eliminating the need for compaction by vibration. Given the highly flowable nature of such concrete, care is required to ensure excellent filling ability and adequate stability. This is especially important in deep structural members and wall elements where concrete can block the flow, segregate and exhibit bleeding and settlement which can result in local defects that can reduce mechanical properties, durability and quality of surface finish. This paper shows results of an investigation of fresh properties of self-compacting concrete, such as filling ability measured by slump flow and flow time (measured by Orimet) and plastic fresh settlement measured in a column. The SCC mixes incorporated various combinations of fine inorganic powders and admixtures. The slump flow of all SCCs was greater than 580 mm and the time in which the slumping concrete reached 500 rnm was less than 3 s. The flow time was less than 5 s. The results on SCCs were compared to a control mix. The compressive strength and splitting tensile strength of SCCs were also measured. The effects of water/powder ratio, slump and nature of the sand on the fresh settlement were also evaluated. The volume of coarse aggregate and the dosage of superphsticizer were kept constant. It can be concluded that the settlement of fresh self-compacting concrete increased with the increase in water/powder ratio and slump. The nature of sand influenced the maximum settlement.

A new method of measuring plastic limit of fine materials

Index properties such as the liquid limit and plastic limit are widely used to evaluate certain geotechnical parameters of fine-grained soils. Measurement of the liquid limit is a mechanical process, and the possibility of errors occurring during measurement is not significant. However, this is not the case for plastic limit testing, despite the fact that the current method of measurement is embraced by many standards around the world. The method in question relies on a fairly crude procedure known widely as the ‘thread rolling' test, though it has been the subject of much criticism in recent years. It is essential that a new, more reliable method of measuring the plastic limit is developed using a mechanical process that is both consistent and easily reproducible. The work reported in this paper concerns the development of a new device to measure the plastic limit, based on the existing falling cone apparatus. The force required for the test is equivalent to the application of a 54 N fast-static load acting on the existing cone used in liquid limit measurements. The test is complete when the relevant water content of the soil specimen allows the cone to achieve a penetration of 20 mm. The new technique was used to measure the plastic limit of 16 different clays from around the world. The plastic limit measured using the new method identified reasonably well the water content at which the soil phase changes from the plastic to the semi-solid state. Further evaluation was undertaken by conducting plastic limit tests using the new method on selected samples and comparing the results with values reported by local site investigation laboratories. Again, reasonable agreement was found.

Alkali-metal salts of aromatic carboxylic acids: Liquid crystals without flexible chains

The alkali-metal salts of meta-substituted benzoic acids exhibit a smectic A mesophase at high temperatures. These compounds are examples of liquid crystals without terminal alkyl chains. The influence of the metal ion and of the type of substituents on the transition temperatures is discussed. Compounds with the substituent in the ortho- and para-positions are non-mesomorphic. The crystal structures of the compounds Rb(C7H4ClO2)(C7H4ClO2H), Na(C7H4IO2)(H2O), K(C7H4ClO2)(C7H4ClO2H) and Rb(C7H4BrO2)(C7H4BrO2H) have been determined by X-ray crystallography. These compounds possess a layerlike structure in the solid state. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Discussion on: Sivakumar, V., Glynn, D., Cairns, P. & Black, J.A. (2009). A new method of measuring plastic limit of fine materials. Géotechnique 59, No. 10, 813-823. by Brendan C. O'Kelly

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An elasto-plastic critical state framework for unsaturated soil.

Data from a series of controlled suction triaxial tests on samples of compacted speswhite kaolin were used in the development of an elasto–plastic critical state framework for unsaturated soil. The framework is defined in terms of four state variables: mean net stress, deviator stress, suction and specific volume. Included within the proposed framework are an isotropic normal compression hyperline, a critical state hyperline and a state boundary hypersurface. For states that lie inside the state boundary hypersurface the soil behaviour is assumed to be elastic, with movement over the state boundary hypersurface corresponding to expansion of a yield surface in stress space. The pattern of swelling and collapse observed during wetting, the elastic–plastic compression behaviour during isotropic loading and the increase of shear strength with suction were all related to the shape of the yield surface and the hardening law defined by the form of the state boundary. By assuming that constant–suction cross–sections of the yield surface were elliptical it was possible to predict test paths for different types of triaxial shear test that showed good agreement with observed behaviour. The development of shear strain was also predicted with reasonable success, by assuming an associated flow rule.