Polarized light and X-ray precession study of the ferroelastic domains of YBa2Cu3O7-δ

The ferroelastic domains of the orthorhombic phase of YBa₂Cu₃O_7- have been observed in polarized light on ceramics and single crystals. By combining polarized light microscopy with the X-ray precession technique, the correlation of the orientation of the orthorhombica- andb-axes with that of thea-b-plane bireflectance, reflection dichroism, transmission dichroism (at a thickness of about 1m), reflection tints generated with compensators and upon uncrossing of polars, as well as the orientation of etch pits has been realized on ferroelastic single domains, bi-domains and more complicated domain patterns. Four ferroelastic orthorhombic domain states have been identified, at variance with former group theoretical considerations, predicting only two states. Ensembles of lamellar domains beyond optical resolution generate strong bireflectance with principal axes rotated by 45° relative to the truea, b-directions.     

Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

DTA/TG coupling

With the discovery of high temperature superconductivity an extraordinary field for investigations on new materials containing up to (more than) 8 or 9 components has been open. But, in addition to problems specifically related to superconductivity, we are faced with a prelimary difficulty: the preparation of well defined compounds which may have reproducible properties. This difficulty is smoothed out when the phase relations in the relevant systems are known. Differential Thermal Analysis (DTA) contributes to their establishment. However, in multicomponent systems, an isopletic line is expected to intercept various boundary surfaces and the analysis is obviously complicated, compared to low order systems. In addition, by the nature of high temperature superconductors the oxygen partial pressure used for their preparation is an important thermodynamic parameter which contributes to fix the oxygen content in the solid state. During heat treatments, the composition of the systems may change, due to oxygen or volatile oxides (Tl₂O₃, PbO₂ or HgO) release. A permanent composition control then requires thermogravimetric (TG) measurements associated to DTA.This paper attempts to demonstrate the efficiency of the assembly DTA/TG for the study of high temperature superconductors. Going beyond the frame of preparation and quality control, the system is also particularly useful for kinetic studies. Examples will be principally in the (Tl,Pb)-(Ba,Sr)-Ca-Cu-O systems.It is a pleasure to associate to this lecture my colleagues from research groups with which I collaborate from many years in the difficult field of elaboration and characterization of thalliumbased HTSC: T. K. Jondo, K. Lebbou. R. Abraham and M. T. Cohen-Adad in Lyon (Lab. PCM2), M. Couach and A. F. Khoder at the CEN in Grenoble (SPSMS), J. Muller and R. Flukiger at the DPMC in Geneva and of course C. Opagiste and Ph. Galez at the LSM in Annecy.     

Synthesis design and structure of a multipore zeolite with interconnected 12- and 10-MR channels

A new molecular sieve, ITQ-38, containing interconnected large and medium pores in its structure has been synthesized. The rational combination of dicationic piperidine-derivative molecules as organic structure directing agents (OSDAs) with germanium and boron atoms in alkaline media has allowed the synthesis of ITQ-38 zeolite. High-resolution transmission electron microscopy (HRTEM) has been used to elucidate the framework topology of ITQ-38, revealing the presence of domains of perfect ITQ-38 crystals as well as very small areas containing nanosized ITQ-38/ITQ-22 intergrowths. The structure of ITQ-38 is highly related to ITQ-22 and the recently described polymorph C of ITQ-39 zeolite. It shares a common building layer with ITQ-22 and contains the same building unit as the polymorph C of ITQ-39. All three structures present similar framework density, 16.1 T atoms/1000 ?(3).