Photochemistry of .alpha.,.beta.-unsaturated thiones: addition to electron-rich olefins from T1

1,1,3-Trimethyl-2-thioxo-1,2-dihydronaphthale(1n)e adds to electron-rich olefins upon excitation to either Sz (PP*) or Sl (ns*) states. Excitation to S2 level resulted in the same mixture of products, namely thietane and 1,4-dithiane, as on excitation to S1 level. Addition occurs to the thiocarbonyl function and not to the carbon-carbon double bond. The addition is site-specific, and the formation of thietane is regiospecific. The ratio of thietane to 1,4-dithiane in the product mixture is dependent on the concentration of the thioenone. The addition is suggested to originate from the lowest triplet state (Tl) and involves diradical intermediates.

Design of Single-Input-Single-Output Compliant Mechanisms for Practical Applications Using Selection Maps

We present an interactive map-based technique for designing single-input-single-output compliant mechanisms that meet the requirements of practical applications. Our map juxtaposes user-specifications with the attributes of real compliant mechanisms stored in a database so that not only the practical feasibility of the specifications can be discerned quickly but also modifications can be done interactively to the existing compliant mechanisms. The practical utility of the method presented here exceeds that of shape and size optimizations because it accounts for manufacturing considerations, stress limits, and material selection. The premise for the method is the spring-leverage (SL) model, which characterizes the kinematic and elastostatic behavior of compliant mechanisms with only three SL constants. The user-specifications are met interactively using the beam-based 2D models of compliant mechanisms by changing their attributes such as: (i) overall size in two planar orthogonal directions, separately and together, (ii) uniform resizing of the in-plane widths of all the beam elements, (iii) uniform resizing of the out-of-plane thick-nesses of the beam elements, and (iv) the material. We present a design software program with a graphical user interface for interactive design. A case-study that describes the design procedure in detail is also presented while additional case-studies are posted on a website. DOI:10.1115/1.4001877].

Antimicrobial activity of highly stable silver nano particles embedded in agar-agar matrix as a thin film

Highly stable silver nanoparticles (Ag NPs) in agar-agar (Ag/agar) as inorganic-organic hybrid were obtained as free-standing film by in situ reduction of silver nitrate by ethanol. The antimicrobial activity of Ag/agar film on Escherichia coli (E. coil), Staphylococcus aureus (S. aureus), and Candida albicans (C albicans) was evaluated in a nutrient broth and also in saline solution. In particular, films were repeatedly tested for antimicrobial activity after recycling. UV-vis absorption and TEM studies were carried out on films at different stages and morphological studies on microbes were carried out by SEM. Results showed spherical Ag NPs of size 15-25 nm, having sharp surface plasmon resonance (SPR) band. The antimicrobial activity of Ag/agar film was found to be in the order, C. albicans > E. coil > S. aureus, and antimicrobial activity against C. albicans was almost maintained even after the third cycle. Whereas, in case of E. coil and S. aureus there was a sharp decline in antimicrobial activity after the second cycle. Agglomeration of Ag NPs in Ag/agar film on exposure to microbes was observed by TEM studies. Cytotoxic experiments carried out on HeLa cells showed a threshold Ag NPs concentration of 60 mu g/mL, much higher than the minimum inhibition concentration of Ag NPs (25.8 mu g/mL) for E. coli. The mechanical strength of the film determined by nanoindentation technique showed almost retention of the strength even after repeated cycle. (C) 2010 Elsevier Ltd. All rights reserved.

Rätt som argument : Leo Mechelin och finska frågan 1886-1912

Right as an Argument. Leo Mechelin and the Finnish Question 1886-1912 At the turn of the 20th century the Finnish Question rose up as a political and juridical issue at the international arena. The vaguely précised position of Finland in the Russian empire led to diverse conclusions concerning the correctness of the February manifesto of 1899. It was predominantly among a European elite of politicians, cultural workers and academics the issue rose some interest. Finns were active making propaganda for their cause, and they put an emphasis on the claim that the right was on the Finnish side. In the study Elisabeth Stubb compare the Finnish, Russian and European statements about the Finnish Question and analyse their use of right as an argument. The Finnish Question offers at the same time a case study of a national entity which possesses a political sphere of life but is not fully independent, and its possibilities to drive its interests in an international context. Leo Mechelin (1839-1914), the leader of the Finnish propaganda organization abroad, is used as a point of departure. The biographical stance is formed into a triangle, where Leo Mechelin, the idea of right and the Finnish Question abroad are the three cornerstones. The treatment of one cornerstone sheds a ligth on the two others. The metaphor of triangulation also worked as a method to reach "a third stance" in a scinetific and political issue that usually is polarised into two opposite alternatives. An adherence to a strict legal right could not in the end offer a complete, unquestionable and satisfactory solution to the Finnsih Question, it was dependent on "the right of state wisdom and sound insight". The Finnish propaganda abroad used almost completely alternative ways of making politics. The propaganda did not have a decisive effect on countries' official politics, but gained unofficial support, especially in the public opinion and in academic statements. Mechelin claimed that the political field was dependent on public opinion and scientific research. Together with the official politics these two fields formed a triangle that shared the task of balancing the political arena and preventing it from making unwise decisions of taking an unjust turn. The international sphere worked as a balancing part in the Finnish Question. Mechelin tried by claiming the status of state for Finland's part to secure the country a place at the official international arena. At the same time, and especially when the claim was not fully adopted, he emphasised, and in a European context worked for, that right would become the guiding light not only for international relations, but also for the policy making in the inner life of the state.

Criteria for prediction of flow instabilities and microstructural manifestations during warm working of AISI 304L stainless steel

The deformation characteristics of 304L stainless steel in compression in the temperature range 20–700°C and strain rate range 0·001–100 s−1 have been studied with the aim of characterising the .flow instabilities occurring in the microstructure. At higher temperatures and strain rates the stainless steel exhibits flow localisation, whereas at temperatures below 500°C and strain rates lower than 0·1 s−1 the flow instabilities are due to dynamic strain aging. Strain induced martensite formation is responsible for the flow instabilities at room temperature and low strain rates (0·01 s−1). In view of the occurrence of these instabilities, cold working is preferable to warm working to achieve dimensional tolerance and reproducible properties in the product. Among the different criteria tested to explain the occurrence of instabilities, the continuum criterion, developed on the basis of the principles of maximum rate of entropy production and separability of the dissipation function, predicts accurately all the above instability features.

Influence of cast versus wrought microstructure on the processing map for hot working of stainless steel type AISI 304

Processing maps for hot working of as-cast and wrought stainless steels of type AISI 304 have been developed in the temperature range 600 to 1250°C and strain rate range 0.001 to 100 s−1. The domain of dynamic recrystallization (DRX) in as-cast material occurs at higher temperatures (1250°C) and lower strain rates (0.001 s−1) than in the wrought steel (1100°C and 0.01 s−1). The effect is explained in terms of enhanced nucleation rate of DRX due to the carbide, ferrite particles, stable oxides/nitrides and second-phase intermetallics in the as-cast microstructure. The DRX domain is wider in the wrought material although the peak efficiency is less (32%) than in the as-cast case (40%). The flow instability regime is not significantly affected by the initial microstructure

Influence of state of stress on the processing map for hot working of stainless steel type AISI 304L: compression vs. torsion

Processing maps for hot working of stainless steel of type AISI 304L have been developed on the basis of the flow stress data generated by compression and torsion in the temperature range 600–1200 °C and strain rate range 0.1–100 s−1. The efficiency of power dissipation given by 2m/(m+1) where m is the strain rate sensitivity is plotted as a function of temperature and strain rate to obtain a processing map, which is interpreted on the basis of the Dynamic Materials Model. The maps obtained by compression as well as torsion exhibited a domain of dynamic recrystallization with its peak efficiency occurring at 1200 °C and 0.1 s−1. These are the optimum hot-working parameters which may be obtained by either of the test techniques. The peak efficiency for the dynamic recrystallization is apparently higher (64%) than that obtained in constant-true-strain-rate compression (41%) and the difference in explained on the basis of strain rate variations occurring across the section of solid torsion bar. A region of flow instability has occurred at lower temperatures (below 1000 °C) and higher strain rates (above 1 s−1) and is wider in torsion than in compression. To achieve complete microstructure control in a component, the state of stress will have to be considered.

Processing map for hot working of stainless steel type AISI 316L

Processing and instability maps using a dynamic materials model have been developed for stainless steel type AISI 316L in the temperature range 600-1250-degrees-C and strain rate range 0.001-100 s-1 with a view to optimising its hot workability. Stainless steel type AISI 316L undergoes dynamic recrystallisation, with a peak efficiency of 35% at 1250-degrees-C and 0.05 s-1, which are the optimum parameters for hot working this material. The material undergoes dynamic recovery at 900-degrees-C and 0.001 s-1. The increase in the dynamic recrystallisation and dynamic recovery temperatures in comparison with stainless steel type AISI 304L is attributed to the presence of a backstress caused by the molybdenum additions. These results are in general agreement with those reported elsewhere on stainless steel type 316 deformed in hot extrusion and hot torsion. At temperatures < 850-degrees-C and strain rates > 10 s-1, the material exhibits flow localisation owing to adiabatic shear band formation, whereas at higher temperatures (> 850-degrees-C) and strain rates (> 10 s-1) mechanical twinning and wavy slip bands are observed. (C) 1993 The Institute of Materials.

Transformation formula for exponential sums involving fourier coefficients of modular forms

In 1984 Jutila [5] obtained a transformation formula for certain exponential sums involving the Fourier coefficients of a holomorphic cusp form for the full modular group SL(2, Z). With the help of the transformation formula he obtained good estimates for the distance between consecutive zeros on the critical line of the Dirichlet series associated with the cusp form and for the order of the Dirichlet series on the critical line, [7]. In this paper we follow Jutila to obtain a transformation formula for exponential sums involving the Fourier coefficients of either holomorphic cusp forms or certain Maass forms for congruence subgroups of SL(2, Z) and prove similar estimates for the corresponding Dirichlet series.

High-temperature low-cycle fatigue behavior of a NIMONIC PE-16 superalloy—Correlation with deformation and fracture

Low-cycle fatigue (LCF) responses of NIMONIC PE-16 for various prior microstructures and strain amplitudes have been evaluated and the fatigue behavior has been explained in terms of the operative deformation mechanisms. Total strain-controlled LCF tests were performed at 923 K on samples possessing three different prior microstructures: alloy A in solution-annealed condition (free of γ′ and carbides), alloy B with double aging treatment (spherical γ′ of 18-nm diameter and M23C6), and alloy C with another double aging treatment (γ′ of size 35 nm, MC and M23C6). All three microstructures exhibited an intial cyclic hardening followed by a period of gradual softening at 923 K. Coffin-Manson plots describing the plastic strain amplitudevs number of reversals to failure showed that alloy A had maximum fatigue life while C showed the least. Alloy B exhibited a two-slope behavior in the Coffin-Manson plot over the strain amplitudes investigated. This has been ascribed to the change in the degree of homogeneity of deformation at high and low strain amplitudes. Transmission electron microscopic studies were carried out to characterize the various deformation mechanisms and precipitation reactions occurring during fatigue testign. Fresh precipitation of fine γ′ was confirmed by the development of “mottled contrast” in alloy C. Evidence for the shearing of the ordered γ′ precipitates was revealed by the presence of superdislocations in alloy C. Repeated shearing during cyclic loading led to the reduction in the size of the γ′ and consequent softening. Coarser γ′ precipitates were associated with Orowan loops. The observed fatigue behavior has been rationalized based on the micromechanisms stated above and on the degree of homogenization of slip assessed by slipband spacing measurements on tested samples.

Effect of strain rate on the high-temperature low-cycle fatigue properties of a nimonic PE-16 superalloy

Strain-rate effects on the low-cycle fatigue (LCF) behavior of a NIMONIC PE-16 superalloy have been evaluated in the temperature range of 523 to 923 K. Total-strain-controlled fatigue tests were per-formed at a strain amplitude of +/-0.6 pct on samples possessing two different prior microstructures: microstructure A, in the solution-annealed condition (free of gamma' and carbides); and microstructure B, in a double-aged condition with gamma' of 18-nm diameter and M23C6 carbides. The cyclic stress response behavior of the alloy was found to depend on the prior microstructure, testing temperature, and strain rate. A softening regime was found to be associated with shearing of ordered gamma' that were either formed during testing or present in the prior microstructure. Various manifestations of dynamic strain aging (DSA) included negative strain rate-stress response, serrations on the stress-strain hysteresis loops, and increased work-hardening rate. The calculated activation energy matched well with that for self-diffusion of Al and Ti in the matrix. Fatigue life increased with an increase in strain rate from 3 x 10(-5) to 3 x 10(-3) s-1, but decreased with further increases in strain rate. At 723 and 823 K and low strain rates, DSA influenced the deformation and fracture behavior of the alloy. Dynamic strain aging increased the strain localization in planar slip bands, and impingement of these bands caused internal grain-boundary cracks and reduced fatigue life. However, at 923 K and low strain rates, fatigue crack initiation and propagation were accelerated by high-temperature oxidation, and the reduced fatigue life was attributed to oxidation-fatigue interaction. Fatigue life was maximum at the intermediate strain rates, where strain localization was lower. Strain localization as a function of strain rate and temperature was quantified by optical and scanning electron microscopy and correlated with fatigue life.