The termination mechanism for radical oligomerization of methacrylonitrile

Summary Decomposition of azobisisobutyronitrile in benzene containing small amounts of methacrylonitrile produces a mixture of oligomers of methacrylonitrile. Analysis by gas chromatography-mass spectrometry indicates that combination is the preponderant (>90%) termination mechanism.     

Anodic oxidation of Co(II) complexes with amines on a rotating Au electrode: Ligand effects in relation to the application for autocatalytic metal deposition

For the comparison of the electrochemical activity of Co(II)-amine complexes, the electrochemical response of an Au rotating disk electrode in alkaline Co(II)-glycine solutions to six amines: ethylenediamine (en), propane-1,2-diamine (pn-1,2), propane-1,3-diamine (pn-1,3), cyclohexane-1,2-diamine (chn), butane-1,4-diamine (bn), diethylenetriamine (dien), was studied. Addition of amines tested (except for bn) in mM levels shifts the open-circuit potential to more negative values by up to 0.5 V and enhances dramatically the anodic Co(II) oxidation current, as a result of Co(II) complex transformation into more stable and electrochemically active Co(II)-amine species. The effect of amines on the open-circuit potential changes in the line: dien ∼ en > pn-1,2 ∼ chn > pn-1,3 ? bn, and on the anodic current in the sequence: dien ∼ en > pn-1,2 > chn > pn-1,3 ? bn. The procedure described helps to select ligands for Co(II) complexes used as reducing agents in electroless plating solutions. The amines of high electrochemical response: dien, en, pn-1,2, and possibly, chn, are suitable for electroless copper deposition, pn-1,3 (a lower response), for electroless silver deposition, and bn (no response), not suitable for electroless plating solutions.     

Efficient technique for constitutive analysis of reinforced concrete flexural members

One of the most difficult issues in the theory of reinforced concrete (RC) is an adequate modelling of deformation behaviour, cracking and, particularly, post-cracking behaviour, as one of the major sources of non-linearity. Applying the concept of average cracking and average strains, deformation behaviour of RC can be modelled by stress–strain tension–stiffening relationships. The authors proposed an innovative inverse technique for constitutive modelling of flexural RC elements. The technique is based on the smeared crack approach and layer model of RC section. The inverse technique aims at deriving tension–stiffening constitutive models from experimental moment–curvature diagrams. The present analysis takes into account the shrinkage effect that is often neglected in other studies. Based on the inverse technique, free-of-shrinkage tension–stiffening relationships are derived using test data of shrunk RC beams. Examples of the application for the analysis of the experimental data obtained by the authors are presented to illustrate the calculation efficiency of the proposed technique.     

Formamidinium‐Based Dion‐Jacobson Layered Hybrid Perovskites: Structural Complexity and Optoelectronic Properties

Layered hybrid perovskites have emerged as a promising alternative to stabilizing hybrid organic–inorganic perovskite materials, which are predominantly based on Ruddlesden‐Popper structures. Formamidinium (FA)‐based Dion‐Jacobson perovskite analogs are developed that feature bifunctional organic spacers separating the hybrid perovskite slabs by introducing 1,4‐phenylenedimethanammonium (PDMA) organic moieties. While these materials demonstrate competitive performances as compared to other FA‐based low‐dimensional perovskite solar cells, the underlying mechanisms for this behavior remain elusive. Here, the structural complexity and optoelectronic properties of materials featuring (PDMA)FA_n–1Pb_nI_3n+1 (n = 1–3) formulations are unraveled using a combination of techniques, including X‐ray scattering measurements in conjunction with molecular dynamics simulations and density functional theory calculations. While theoretical calculations suggest that layered Dion‐Jacobson perovskite structures are more prominent with the increasing number of inorganic layers (n), this is accompanied with an increase in formation energies that render n > 2 compositions difficult to obtain, in accordance with the experimental evidence. Moreover, the underlying intermolecular interactions and their templating effects on the Dion‐Jacobson structure are elucidated, defining the optoelectronic properties. Consequently, despite the challenge to obtain phase‐pure n > 1 compositions, time‐resolved microwave conductivity measurements reveal high photoconductivities and long charge carrier lifetimes. This comprehensive analysis thereby reveals critical features for advancing layered hybrid perovskite optoelectronics.     

Peculiarities of Starch Cationization with Glycidyltrimethylammonium Chloride

Cationic starch derivatives containing quaternary ammonium groups with high degree of substitution are prepared by reaction of starch with glycidyltrimethylammonium chloride (GTAC) in different reaction media. In aqueous solutions of GTAC along with conventional hydrolysis of epoxy groups, their interaction with chloride ions also takes place. This resulted in formation of hydroxyl ions which accelerate both the hydrolysis of GTAC epoxy groups and can act as the internal catalyst in the reaction of GTAC with starch. Therefore, even in the absence of the external catalyst, cationic starch with a high degree of substitution can be obtained. The autocatalytic reaction of GTAC with starch proceeds more rapidly at higher temperatures but with lower reaction efficiency. Both in the absence of the external catalyst and in the case when sodium alkali is used as a catalyst the reaction of starch with GTAC proceeds only when a particular quantity of “free” water is present in the system. When the NaOH as catalyst is used the reaction efficiency is about 90%. The yield of starch cationization reaction decreases when the quantity of “free” water is twice or thrice higher than required for starch modification to begin.     

Structural integrity analysis of an Ignalina nuclear power plant building subjected to an airplane crash

Recent terrorist attacks using commandeered commercial airliners on civil structures have raised the issue of the ability of nuclear power plants to survive the consequences of an airliner crash. The structural integrity analysis due to the effects of an aircraft crash on an Ignalina nuclear power plant (INPP) accident localization system (ALS) building is the subject of this paper. A combination of the finite element method and empirical relationships were used for the analysis. A global structural integrity analysis was performed for a portion of the ALS building using the dynamic loading from an aircraft crash impact model. The local effects caused by impact of the aircraft's engine on the building wall were evaluated independently by using an empirical formula.The results from the crash analysis of a twin engine commercial aircraft show that the impacted reinforced concrete wall of the ALS building will not have through-the-wall concrete failure, and the reinforcement will not fail. Strain-rate effects were found to delay the onset of cracking. Therefore, the structural integrity of the impacted wall of the INPP ALS building will be maintained during the crash event studied.     

Monitoring the Mechanical and Structural Behavior of the Pavement Structure Using Electronic Sensors

Over the last decade, pavement instrumentation has become an important tool for monitoring the performance of pavement structures and materials under real climatic and traffic conditions. Stress, strain transducers, loop profilers, temperature, and moisture sensors could be reasonably used for sophisticated analysis of pavement performance. Commonly, such research projects involve only few pavement structures under accelerated loading tests. The unique experimental road section was constructed in 2007 in Lithuania. It consists of 27 different flexible pavement structures and all necessary electronic sensors. This road is affected by real climatic conditions and high‐intensity heavy vehicle traffic. The aim of such research is to continuously monitor performance of different pavement structures and to elaborate on the most suitable and economically effective pavement structures.     

Analysis of decay heat removal from RBMK-1500 reactor in decommissioning phase by natural circulation of water and air

The main problem in nuclear energy is providing of safety at all stages of lifetime of nuclear installations in conditions of normal operation, accidents and at shutdown. Ignalina NPP, located in Lithuania, is one of the latest with RBMK reactors at highest capacity. Ignalina NPP has two units, both are closed for decommissioning now (in 2004 and 2009). Both units are equipped with RBMK-1500 reactors, the thermal power output is 4200 MW, the electrical power capacity is 1500 MW for each. In RBMK-1500 reactor the fuel assemblies remain for long time inside reactor core after the final shutdown. The paper discusses possibility of heat removal from the RBMK-1500 core at shutdown condition by natural circulation of water (1) and air (2) inside the fuel channels. In first case the decay heat from fuel assemblies is removed due to natural circulation of water and the piping above reactor core should be cooled by means of ventilation in the drum separator compartments. To warrant free access of air in to fuel channels (in the second case) the reactor cooling system should be completely dry out and the pressure headers and the steam discharge valves in steam lines should be opened. If mentioned conditions will be fulfilled, the reactor core will be cooled by natural circulation of water or air and fuel rods remain intact.