Calorimetric study and thermodynamic description of Ga-Ge-Li liquid alloys

This publication contains the thermodynamic results received by the drop calorimetry method. The experiments were conducted for four different cross sections, at the temperature of 1080 K. The investigated alloys were as follows: (Ga_0.75Li_0.25)_1-xGe_x, (Ge_0.50Li_0.50)_1-xGa_x, (Ga_0.50Li_0.50)_1-xGe_x, (Ga_0.25Li_0.75)_1-xGe_x. The mixing enthalpy changes measured for all four cross sections of the Ga-Ge-Li system are characterized by negative deviations from the ideal solutions. The Muggianu model with the ternary interaction parameters was applied to elaborate the experimental data of the mixing enthalpy change with the use of the optimized thermodynamic parameters of the binary systems available in the literature.     

High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr₂O₃ is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr)₂O₄ phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C₁₂A₇, CA, CA₂ and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr^III)₂O₄ spinel mainly transformed into hauyne (Ca₄Al₆Cr^VIO₁₆) and Ca₅Cr₃O₁₂ which contains both Cr(IV) and Cr(VI). The reaction of C₁₂A₇ and CA with the spinel phase also resulted in the formation of Ca₄Al₆CrO₁₆. Conversely, the reaction of Mg(Al,Cr^III)₂O₄ spinel with CA₂ resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr^III)₂O₄ reacted with either C₁₂A₇ or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr^III)₂O₄ reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca₅Cr₃O₁₂ dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA₂, even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr)₂O₄ is very stable and does not leach in either distilled water or acidic solution.     

Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber

The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel oxidation is assumed to be 1,400 °C while the pressure for carburetor and diesel engines is assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel and methane at the excess air coefficient corresponding to the fuel oxidation temperature of 1,400 °C. In the paper, the method for calculating the equilibrium composition based on the equilibrium constant and mass conservation equations has been applied. It is shown that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to 80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an increase in NO₂. The formation of NO may be not affected by the increase in pressure by virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO₂) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.     

Roughing,semi-finishing and finishing of laser surface modified nickel bonded NbC and WC inserts for grey cast iron (GCI) face-milling

An attempt to improve the machining performance of NbC-Ni cutting inserts by rapid pulse electric current sintering (PECS), TiC and Mo₂C additions and laser surface modification (LSM) was done. Use of a nickel binder and additions TiC and Mo₂C to liquid phase sintered (LPS) NbC based samples led to comparable hardness (>13 GPa) and K_IC (~10 MPa.m^1/2) to LPS WC-Co/Ni samples. The laser surface modification (LSM) technique produced a ~2.5 μm thick self-carbide coating, increasing the surface hardness of all the samples. Laser surface modification was done to improve abrasion and attrition wear resistance. Face-milling of grade 17 grey cast iron (BS 1452/GG35) was conducted at 100–500 m/min cutting speeds (v_c) and 0.25–1.5 mm depths of cut (a_p). The insert wear was measured after every pass, and analyzed by annular dark field scanning transmission electron microscopy (ADF-STEM). During roughing, WC-Co based inserts had the lowest flank wear rate (FWR) values, with the WC-10Co (LPS) insert having a FWR of 10.15 μm/min after 20 min cutting time. However, during semi-finishing and finishing, NbC-4TiC-12Ni (PECS) and NbC-4Mo₂C-4TiC-12Ni (PECS) inserts had the lowest FWR values, showing up to six times longer tool life than the WC-Co (LPS) inserts based inserts and 12 times longer life than the WC-Ni based inserts. Generally, LSM improved the NbC inserts' tool life, reducing the FWR values in all NbC based inserts in all cutting tests.     

Thermal expansion of CaAl4O7-based refractory compositions containing MgO and CaO additions

Various compositions of recently developed CaAl₄O₇-based ceramics are mentioned with special reference to those called “nonexpansive refractories” (=NER). The observed effect of deep depression of their thermal expansion is mainly ascribed to the creation of a specific microstructure resulting from high temperature reactions of CaAl₄O₇ with MgO or CaO additives yielding a CaAl₂O₄-based liquid. Some details characterizing the phase composition of the reaction zone are given. The effect of the calculated approximate content of CaAl₂O₄ in the specimens is interpreted graphically. Basing on the results of changes in the CaAl₄O₇ single crystal dimensions presented in comparison with some other expansion data, the presumable nature of the specific behavior of NER bodies on heating up to 500 °C is discussed. The NER products fired at 1620 °C are characterized by high strength and low open porosity.     

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.     

Fairness-related challenges in mobile opportunistic networking

The fundamental challenge in opportunistic networking, regardless of the application, is when and how to forward a message. Rank-based forwarding techniques currently represent one of the most promising methods for addressing this message forwarding challenge. While these techniques have demonstrated great efficiency in performance, they do not address the rising concern of fairness amongst various nodes in the network. Higher ranked nodes typically carry the largest burden in delivering messages, which creates a high potential of dissatisfaction amongst them. In this paper, we adopt a real-trace driven approach to study and analyze the trade-offs between efficiency, cost, and fairness of rank-based forwarding techniques in mobile opportunistic networks.Our work comprises three major contributions. First, we quantitatively analyze the trade-off between fair and efficient environments. Second, we demonstrate how fairness coupled with efficiency can be achieved based on real mobility traces. Third, we propose FOG, a real-time distributed framework to ensure efficiency–fairness trade-off using local information. Our framework, FOG, enables state-of-the-art rank-based opportunistic forwarding algorithms to ensure a better fairness–efficiency trade-off while maintaining a low overhead. Within FOG, we implement two real-time distributed fairness algorithms; Proximity Fairness Algorithm (PFA), and Message Context Fairness Algorithm (MCFA). Our data-driven experiments and analysis show that mobile opportunistic communication between users may fail with the absence of fairness in participating high-ranked nodes, and an absolute fair treatment of all users yields inefficient communication performance. Finally our analysis shows that FOG-based algorithms ensure relative equality in the distribution of resource usage among neighbor nodes while keeping the success rate and cost performance near optimal.     

Generalizing the CHOKe flow protection

This paper proposes a simple and stateless active queue management (AQM) scheme, called geometric CHOKe (gCHOKe), to protect responsive flows from unresponsive ones. gCHOKe has its root in and is a generalization of the original CHOKe. It provides an additional power of protection, achieved by introducing an extra flow matching trial following each successful flow comparison of packets. The maximum number of comparisons permitted for an arrival can be controlled by a parameter called maxcomp. The quality of flow protection improves with maxcomp. Compared to the plain CHOKe (which is just the simplest case of gCHOKe), our analysis and simulations show that the scheme can achieve over 20% improvement in the bounds of both bandwidth and buffer space used by an aggressive flow. In addition, up to 14% of the total link capacity can be saved from the unresponsive flow, allowing responsive or rate-adaptive flows to obtain a better share of resources in the router.