Bronze roman mirrors: the secret of brightness

The surface microchemical structure of high tin leaded bronze Roman mirrors has been studied by means of scanning electron microscopy combined with energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and optical microscopy (OM) techniques. The results allowed understanding of the origin of their high chemical stability and silvery-lustrous appearance. Indeed, some areas of the selected Roman mirrors are still characterised by a highly reflective and silver coloured surface even though they have been buried in the soil for about 2000 years. The micro-chemical results obtained from these areas have revealed that the mirror surface was tin enriched via inverse-segregation phenomenon by tailoring the cooling parameters. Furthermore, the presence of tin could be likely enhanced via cycles of oxidation and selective copper corrosion processes, thus resulting in a tin surface enrichment as a semi-transparent amorphous-like tin oxide (SnO₂) film, as well as a copper depletion at the outer surfaces.     

Microchemical Investigation of Archaeological Copper Based Artefacts Disclosing an Ancient Witness of the Transition from the Value of the Substance to the Value of the Appearance

In many Italian archaeological sites dated between the sixth and third centuries BC, unworked lumps of Cu-based materials are sometimes found, the so called Aes Rude, which according to archaeological considerations were appreciated as currency, as a medium of exchange and as a form of saving. The microchemical investigation of these ancient artefacts discloses their nature as apparently not usable for any functional applications or possible use. Indeed, Aes Rude resemble ordinary copper material, but microchemical results indicate that they are constituted by highly ferruginous leaded copper, making them useless for producing other metal objects by means of casting or hot and cold working. Notwithstanding this intrinsic negative feature, the production of these intractable Cu-based alloys was deliberately carried out to maximise the process yield in terms of produced metal from an impure and unselected metal ore by tailoring the smelting process parameters. With these considerations in mind, the microchemical investigation of these ancient iron–copper alloys gives evidence of the passage from the acceptance of an artefact value based on its true nature or potential use to the acceptance of the value based only on its appearance or form irrespective of its present or future use. This information could contribute to a better understanding of the evolution of human thought and economic and social interactions.     

Sub-Ramsey numbers for arithmetic progressions

Letm 3 andk 1 be two given integers. Asub-k-coloring of [n] = {1, 2,...,n} is an assignment of colors to the numbers of [n] in which each color is used at mostk times. Call an arainbow set if no two of its elements have the same color. Thesub-k-Ramsey number sr(m, k) is defined as the minimumn such that every sub-k-coloring of [n] contains a rainbow arithmetic progression ofm terms. We prove that((k – 1)m ²/logmk) sr(m, k) O((k – 1)m ² logmk) asm , and apply the same method to improve a previously known upper bound for a problem concerning mappings from [n] to [n] without fixed points.Research supported in part by Allon Fellowship and by a Bat Sheva de-Rothschild grant.Research supported in part by the AKA Research Fund of the Hungarian Academy of Sciences, grant No. 1-3-86-264.     

Etude par diffraction X et microscopie electronique du système CaTiO3---Ca2Fe2O5

In order to check the extended defect model previously proposed for the nonstoichiometric perovskite A_nM_nO_3n−1 (n 2), the Ca₂Ti_2−2xFe_2xO_6−x solid solution has been studied by means of X-ray diffraction and electron microscope investigations. The results show the existence of a continuous evolution (0 x 1) with two different regions. Close to the CaTiO₃ composition (0 x 0.40) the oxygen vacancies seem to be randomly distributed and the symmetry remains pseudocubic. In the composition range 0.55 x 1, the electron microscope patterns show an ordering of the defects: the oxygen vacancies are ordered in the (0k0) planes in strings parallel to the [101] direction. It is concluded from these observations that perpendicular to the Oy direction isolated planes of tetrahedra arranged in rows separate planes of corner-linked octahedra. The n = 2; 2.5; 3, et 4 terms of the A_nM_nO_3n−1 series have been identified. C.S. planes characteristic of classical nonstoichiometric oxides with small cations do not appear: instead, tetrahedra planes succeed to the previous octahedra planes as the degree of nonstoichiometry increases.

Résumé

Afin de vérifier le modèle de non-stoechiométrie proposé dans un travail précédent pour les perovskites lacunaires A_nM_nO_3n−1 (n 2), la solution solide Ca₂Ti_2−2xFe_2xO_6−x a été, étudiée par diffraction X et microscopie électronique. Les résultats montrent l'existence d'une évolution continue (0 x 1) avec deux domaines différents. Pour les compositions proches de CaTiO₃ (0 x 0.40), les lacunes oxygénées semblent être distribuées statistiquement et la symétrie demeure pseudocubique. Dans le domaine de compositions 0.55 x 1, les images de microscopie électronique montrent un ordre des défauts: les lacunes d'oxygène sont ordonnées dans les plans (0k0) en rangées parallèles à la direction [101]. Ces observations ont permis de conclure que perpendiculairement à la direction Oy des plans isolés de files de tétraèdres séparent des plans d'octaèdres liés par leurs sommets. Les termes n = 2; 2.5; 3 et 4 des séries A_nM_nO_3n−1 ont été identifiés. Des plans de cisaillement rencontrés dans les oxydes non-stoechiométriques classiques de petits cations n'ont pas été mis en évidence: par contre, des plans de tétraèdres se substituent aux plans d'octaèdres initiaux lorsque le degré de non-stoechiométrie augmente.     

Extract-photometric determination of vanadium(V) with 3-indole-acetohydroxamic acid

Summary A spectrophotometric study has been carried out of the violet complex 3-indole-acetohydroxamic acid-vanadium extracted into a solution of trioctylmethyl-ammonium chloride in toluene [_max 525 nm; =5381 l mol^–1 cm^–1; stoichiometry 1:3 (metal:reagent)]. A new method for the extract-spectrophotometric determination of V⁵⁺ in the range of 2–7 g/g is proposed and interferences by foreign ions were investigated. The method has been satisfactorily applied to the determination of vanadium(V) in fuel oil. The relative error is ±2.9%.     

Two combinatorial problems on posets

Bialostocki proposed the following problem: Let nk2 be integers such that k|n. Let p(n, k) denote the least positive integer having the property that for every poset P, |P|p(n, k) and every Z _k -coloring f: P Z _k there exists either a chain or an antichain A, |A|=n and _aA f(a) 0 (modk). Estimate p(n, k). We prove that there exists a constant c(k), depends only on k, such that (n+k–2)²–c(k) p(n, k) (n+k–2)²+1. Another problem considered here is a 2-dimensional form of the monotone sequence theorem of Erdös and Szekeres. We prove that there exists a least positive integer f(n) such that every integral square matrix A of order f(n) contains a square submatrix B of order n, with all rows monotone sequences in the same direction and all columns monotone sequences in the same direction (direction means increasing or decreasing).     

Microdetermination of iodine in carrier-free131I solutions

A photocolorimetric microtechnique is described, by which it is possible to determine the real amount of iodine in carrier-free solutions of¹³¹INa. The method is conceptually based on the well-known effect of iodine, by which the rate of reduction of ceric sulfate by arsenious acid in sulfuric acid solutions is proportional to the iodide concentration. The tittration and the preparation of its corresponding calibration graph require approximately 90 min; thus, it seems possible to use this technique as a routine analysis. Under the stated conditions of temperature and reaction time, it is possible to determine samples of iodine with concentrations ranging between 20 and 160 ng/ml. The standard error between different determinations is less than ±5%. The application of the method in production control and utilization of carrier-free¹³¹I solutions, free from reducing agent, are discussed.     

Easy synthesis of heterocyclic carbene complexes by activation of chalcogenopyrones and benzopyrones to pyrylium salts and subsequent addition of carbanion of methoxy(methyl)pentacarbonyltungsten carbene complex

Methylenechalcogenopyran and benzopyran Fischer carbene complexes are easily obtained from commercially available chalcogenopyrones or benzopyrones and carbanion of methoxy(methyl)carbene tungsten complex. The key of the heterocyclic carbene formation is the activation of the carbonyl group by alkylation with alkyl trifluoromethanesulfonate reagent.     

Structures lamellaires: Syntaxie,polytypie et non-stoechiométrie

The paper recalls elementary principles useful for the understanding of some types of nonstoichiometry in the solid state. The structures of layered compounds are mostly characterized by the existence of layered “molecular” entities exhibiting a simple type of bonding; in between are inserted, depending on the case, cations, anions, structural frameworks, or molecules. The layers have a quaternary or a ternary symmetry; in the last case the structures can be polytypic. The phenomenon of syntaxy occurs between polymorphs or between species with different chemical compositions but with structural affinities (identical atomic planes). In some cases an ordered syntaxy between structural blocks yields the chemical compositions of the multiple phases observed for some nonstoichiometric systems, for instance rare earth ones. Ordered syntaxy and polytypism, which can occur simultaneously, give a regular repetition of structural or chemical elements over very long crystalline distances. Those phenomena of order in solids, as yet unexplained, recall ordering phenomena observed in the scope of biological chemistry.