Enhanced oxidation of the 9%Cr steel P91 in water vapour containing environments

The short term (∼100 h) oxidation behaviour of the 9%Cr steel P91 was studied at 650 °C in N₂-O₂-H₂O gas mixtures containing a relatively low oxygen level of 1%. The oxidation kinetics were measured thermogravimetrically and the oxide scale growth mechanisms were studied using H₂¹⁸O-tracer with subsequent analyses of oxide scale composition and tracer distribution by MCs⁺-SIMS depth profiling. The corrosion products were additionally characterised by light optical microscopy, SEM-EDX and XRD. It was found that the transition from protective, Cr-rich oxide formation into non-protective mixed oxide scales is governed by the ratio H₂O^(g)/O₂ ratio rather than the absolute level of H₂O^(g). The results of the tracer studies in combination with the data obtained from experiments involving in situ gas changes clearly illustrated that under the prevailing conditions the penetration of water vapour molecules triggers the enhanced oxidation and sustains the high growth rates of the poorly protective Fe-rich oxide scale formed in atmospheres with high H₂O^(g)/O₂ ratios. The experimental observations can be explained if one assumes the scale growth to be governed by a competitive adsorption of oxygen and water vapour molecules on external and internal surfaces of the oxide scales in combination with the formation of a volatile Fe-hydroxide during transient oxidation. The formation of the non-protective Fe-rich oxide scales is suppressed in atmospheres with low H₂O^(g)/O₂ -ratios, and the healing of any such scale is promoted.     

Long-term performance of cement paste during combined calcium leaching-sulfate attack: kinetics and size effect

This paper presents experimental results obtained on cement paste samples (water/cement ratio of 0.4) subjected to a low-concentration (15 mmol/l) external sulfate attack during several weeks. Chemical and microstructural analyses include the continuous monitoring of calcium loss and sulfate consumption within the cement paste, periodic layer by layer X-ray diffraction (XRD)/energy-dispersive spectrometer (EDS) analyses of the solid constituents of the cement matrix (ettringite, portlandite, gypsum) within the calcium-depleted part of the samples. Scanning electron microscopy (SEM) and visual observations are used to follow the crack pattern evolution during the external sulfate attack. The relation between the size of the specimen and crack initiation/development is investigated experimentally by performing tests on samples with different thickness/diameter ratios.     

Experimental investigations and thermodynamic modelling of KCl–LiCl–UCl3 system

Experimental investigations and Gibbs energy modelling of KCl–LiCl–UCl₃ system employing CALPHAD method are reported. Gibbs energy modelling of the subsystems KCl–UCl₃ and LiCl–UCl₃ was carried out primarily using phase diagram data from the literature. For the Gibbs energy modelling of the KCl–LiCl subsystem, new phase boundary data corresponding to four terminal compositions $(x_{\mathrm{LiCl}}=0.03$, 0.05, 0.95 and 0.97) obtained through differential thermal analysis data along with thermochemical and phase diagram data from the literature were used. Thermal analysis was also carried out for KCl–LiCl eutectic mixture containing small amounts of UCl₃ $(x_{{\mathrm{UCl}}_3}=9.03\times {10}^{-3}$ and $1.79\times {10}^{-2}$). The liquidus temperatures for these compositions were found to be 637 K and 674 K. Electromotive force data for dilute solutions of UCl₃ in the KCl–LiCl eutectic melt, measured in the temperature range 708–833 K in the present work, were found to be in good agreement with the literature data. These data were also used as input for the Gibbs energy modelling of the KCl–LiCl–UCl₃ system. In order to improve the quality of the resulting Gibbs energy functions of the quasibinaries and the quasiternary, enthalpies of mixing of the corresponding melts estimated using an empirical correlation based on surrounded-ion model were also used as input. Finally, the generated Gibbs energy functions were used to compute phase equilibria.     

Low-sintering ceramic materials based on Bi2O3–ZnO–Nb2O5 compounds

In this work, sintering behaviour of Bi₂O₃–ZnO–Nb₂O₅ compounds was investigated in order to develop LTCC materials with suitable microwave properties. Structure, dielectric properties and sintering were studied for ceramic dielectrics based on the system: Bi₂ZnNb₂O₉ with the pyrochlore structure and ZnNb₂O₆ with a columbite one. The work was carried out over a wide range of initial components concentration. Ceramic samples of these materials were prepared by the mixed oxide technique. The effect of adding glass to the materials have been discussed. The sintering behaviour, dielectric permittivity, quality factor and crystal structures have been characterized for ceramic samples depending on compositions. Low-temperature co-firable ceramic material with ɛ ∼ 30, τ_ɛ = 0 and Q × f = 3500 GHz based on the above system was synthesized.     

Enthalpy of formation and dehydration of lithium and sodium zeolite beta

Zeolite Li-BEA and Na-BEA with Si/Al = 3–4 were synthesized by alumination and ion exchange, then characterized by XRD, TG–DSC and NMR. The enthalpies of formation and dehydration of Li and Na ion exchanged zeolite beta are investigated by high temperature oxide melt solution calorimetry. For Li-BEA, the formation enthalpies of formation from oxides at 25 °C are 25.6 ± 1.7 kJ/mol TO₂ for the dehydrated zeolite and −8.45 ± 0.94 kJ/mol TO₂ for the fully hydrated zeolite; for Na-BEA they are −2.4 ± 0.6 kJ/mol TO₂ for the dehydrated and −17.8 ± 1.0 kJ/mol TO₂ for the fully hydrated zeolite. The integral dehydration enthalpy at 25 °C is 33.2 ± 1.8 kJ/mol H₂O for Li-BEA and 16.5 ± 1.1 kJ/mol H₂O for Na-BEA. The partial molar dehydration enthalpies of both Li-BEA and Na-BEA are a linear function of water content. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents.     

Radiation crosslinking of linear polyethyleneimine-based nanoparticles grafted to poly(glycidyl methacrylate) via trimethylolpropane triacrylate as potential electronic packaging material

Linear polyethyleneimine (L-PEI)-based nanoparticles were synthesized via hydrolysis of poly-2-methyl-2-oxazoline (PMeOx), which was prepared by cationic ring-opening polymerization of the oxazoline five-membered ring. Herein, a kinetic study of the ring-opening polymerization reaction is discussed. The nuclear magnetic resonance spectrum of PMeOx verified the presence of repeating units and terminal groups in the polymer's structure. Molar ratios of PEI and PMeOx were characterized using size exclusion chromatography with low-polydispersity polymer chains as the controlled polymerization reaction. PEI and PMeOx exhibited narrow particle size distribution with hydrodynamic radii of 89 and 67 nm, respectively, as determined via dynamic light scattering analysis. In addition, atomic forces and scanning electron microscopy were used to investigate the topography of the PEI thin films. Poly(glycidyl methacrylate) P(GMA) was grafted onto a PEI chain in the presence of trimethylolpropane triacrylate (TMPTA) as the crosslinking agent to synthesize the P(GMA–PEI–TMPTA) tripolymer via free radical polymerization using gamma irradiation. The thermal characterization of the P(GMA–PEI–TMPTA) tripolymer was conducted using thermogravimetric analysis and differential scanning calorimeter. Generally, the thermal stability of the P(GMA–PEI–TMPTA) tripolymer was improved at low-glycidyl methacrylate concentrations. The prepared tripolymer could be used as effective packaging materials for electronics industries.     

Pressure sintering of W-15wt.%Cu alloys prepared by mechanical alloying as a subsequent densification treatment method

1. Introduction W-Cu alloys are widely used in many fields due to their superior properties [1]. With the rapid de-velopment of technology, more demands are being made on the W-Cu alloys. For instance, higher heat conductivity, lower thermal expansion coefficient, and more rigorous air tightness are required when these alloys are used for electronic package materi-als, such as heat sink materials. Especially, the re-quirement of more rigorous air tightness means that the W-Cu alloys must pos…     

Memory applications of a thiophene-based conjugated polymer by photoluminescence measurements

Data-storage and memory applications of conjugated polymers and organic semiconductors are generally probed by device current or dielectric properties to determine the storage and switching properties. In this article, we use photoluminescence as an alternate method of probing the states of the devices. We have fabricated such devices based on a polythiophene derivative, and recorded photoluminescence (PL) spectra during and after applying bias. The presence of localized charges on the backbone of the polymer has been found to modulate the PL intensity. Since the relaxation of the space charges is slow, we have shown that PL intensity can be used as a probe for memory applications to read the state of the device. PL as a probe for memory applications of polymeric materials offers an intrinsic advantage that the state can be read without affecting the device properties.     

Fatigue crack growth prediction in nuclear piping using Markov chain Monte Carlo simulation

In this paper, we present and demonstrate a methodology to improve probabilistic fatigue crack growth (FCG) predictions by using the concept of Bayesian updating using Markov chain Monte Carlo simulations. The methodology is demonstrated on a cracked pipe undergoing fatigue loading. Initial estimates of the FCG rate are made using the Paris law. The prior probability distributions of the Paris law parameters are taken from the tests on specimen made of the same material as that of pipe. Measured data on crack depth over number of loading cycles are used to update the prior distribution using the Markov chain Monte Carlo. The confidence interval on the predicted FCG rate is also estimated. In actual piping placed in a plant, the measured data can be considered equivalent to the data received from in-service inspection. It is shown that the proposed methodology improves the fatigue life prediction. The number of observations used for updating is found to leave a significant effect on the accuracy of the updated prediction.     

Formulation and Biodistribution of <Superscript>99<Emphasis Type="Italic">m</Emphasis></Superscript>Tc-Dacarbazine,a Radioligand for Neoplasm Imaging

A method for preparing ^99mTc-Dacarbazine, a potential cancer diagnostic agent, was developed. The method is based on direct labeling of Dacarbazine with ^99mTc in the presence of stannous chloride as reducing agent. The reaction conditions were optimized to obtain the radiochemical yield of ^99mTc-Dacarbazine higher than 90%. The biodistribution of ^99mTc-Dacarbazine in normal and tumor-bearing Albino Swiss mice was studied. ^99mTc-Dacarbazine has a high tumor affinity and shows promise for cancer imaging. Quantitative relationship between the optimized structures and computed molecular properties related to Dacarbazine binding sites was analyzed using molecular modeling.