Control of transient thermal response during sequential open-die forging: A trajectory optimization approach

A trajectory optimization approach is applied to the design of a sequence of open-die forging operations in order to control the transient thermal response of a large titanium alloy billet. The amount of time tire billet is soaked in furnace prior to each successive forging operation is optimized to minimize the total process time while simultaneously satisfying constraints on the maximum and minimum values of the billet's temperature distribution to avoid microstructural defects during forging. The results indicate that a "differential" heating profile is the most effective at meeting these design goals.

Nitride synthesis using ammonia and hydrazine - a thermodynamic panorama

Because of the wide variety of projected applications of ultrapure nitrides in advanced technologies, there is interest in developing new cost-effective methods of synthesis. Explored in this study is the use of ammonia and hydrazine for the synthesis of nitrides from oxides, sulfides and chlorides. Even when the standard Gibbs energy change for the nitridation reactions involved are moderately positive, the reaction can be made to proceed by lowering the partial pressure of the product gas below its equilibrium value. Use of a metastable form of precursor in the nanometric size range is an alternative method to facilitate nitridation. Ellingham-Richardson-Jeffes diagrams are used for a panoramic presentation of the driving force for each set of reactions as a function of temperature. Oxides are the least promising precursors for nitride synthesis; sulfides offer a larger synthetic window for many useful nitrides such as BN, AlN, InN, VN, TiN, ThN and Si3N4. The standard Gibbs free energy changes for reactions involving chlorides with either ammonia or hydrazine are much more negative. Hydrazine is a more powerful nitriding agent than ammonia. The metastability of hydrazine requires that it be introduced into a reactor through a water-cooled lance. The use of volatile halides with ammonia or hydrazine offers the potential for synthesis of pure and doped nanocrystalline nitrides. Nitride thin films can also be prepared by suitable adaptations of the chloride route. (C) 2002 Kluwer Academic Publishers.

Optimization of off-oriented Ge substrates for MOVPE-grown GaAs solar cells

GaAs/Ge heterostructures having abrupt interfaces were grown on 2degrees, 6degrees, and 9degrees off-cut Ge substrates and investigated by cross-sectional high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy, photoluminescence spectroscopy and electrochemical capacitance voltage (ECV) profiler. The GaAs films were grown on off-oriented Ge substrates with growth temperature in the range of 600-700degreesC, growth rate of 3-12 mum/hr and a V/III ratio of 29-88. The lattice indexing of HRTEM exhibits an excellent lattice line matching between GaAs and Ge substrate. The PL spectra from GaAs layer on 6degrees off-cut Ge substrate shows the higher excitonic peak compared with 2degrees and 9degrees off-cut Ge substrates. In addition, the luminescence intensity from the GaAs solar cell grown on 6degrees off-cut is higher than on 9degrees off-cut Ge substrates and signifies the potential use of 6degrees off-cut Ge substrate in the GaAs solar cells industry. The ECV profiling shows an abrupt film/substrate interface as well as between various layers of the solar cell structures.

Phase diagram for the system Nd-Mn-O and thermodynamic properties of NdMnO3 and NdMn2O5

Studies on the phase relations in the system Nd-Mn-O at 1223 K showed two stable ternary compounds, NdMnO3 and NdMn2O5. An isothermal section of the ternary phase diagram for the system Nd-Mn-O was constructed based on phase analysis of samples quenched after equilibration using XRPD and EDS. An advanced version of the solid-state cell incorporating a buffer electrode was used to determine the Gibbs energies of decomposition of NdMnO3 and NdMn2O5 in the temperature range from 925 to 1400 K. Pure oxygen gas at 0.1 MPa was used as the reference electrode, and yttria-stabilized zirconia as the solid electrolyte. The buffer electrode was designed to prevent polarization of the three-phase electrode and ensure accurate data. The measured oxygen potential corresponding to the reaction,2 Nd2O3 + 4 MnO + O-2 --> 4 NdMnO3 can be represented by the equation,Amu(o2) / J.mol(-1) (+/-580) = -523 960 + 170.96 (T/K)Similarly, for the formation of NdMn2O5 according to the reaction,3 NdMnO3 + Mn3O4 + O-2 --> 3 NdMn2O5 Amu(o2) / J.mol(-1) (+/-660) = - 269 390 + 181.74 (T/K) (C) 2002 Elsevier Science Ltd. All rights reserved.

Systematic trends in structural and thermodynamic properties of ternary oxides in the systems Ln-Pd-O (Ln = lanthanide element)

Isothermal sections of the phase diagrams for the systems Ln-Pd-O (Ln = lanthanide element) at 1223 K indicate the presence of two inter-oxide compounds Ln(4)PdO(7) and Ln(2)Pd(2)O(5) for Ln = La, Pr, Nd, Sm, three compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) for Ln = Eu, Gd and only one compound of Ln(2)Pd(2)O(5) for Ln = Tb to Ho. The lattice parameters of the compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) show systematic nonlinear variation with atomic number. The unit cell volumes decrease with increasing atomic number. The standard Gibbs energies, enthalpies and entropies of formation of the ternary oxides from their component binary oxides (Ln(2)O(3) and PdO) have been measured recently using an advanced version of the solid-state electrochemical cell. The Gibbs energies and enthalpies of formation become less negative with increasing atomic number of Ln. For all the three compounds, the variation in Gibbs energy and enthalpy of formation with atomic number is markedly non-linear. The decrease in stability with atomic number is most pronounced for Ln(2)Pd(2)O(5), followed by Ln(4)PdO(7) and Ln(2)PdO(4). This is probably related to the repulsion between Pd2+ ions on the opposite phases Of O-8 cubes in Ln(2)Pd(2)O(5), and the presence of Ln-filled O-8 cubes that share three faces with each other in Ln4PdO7. The values for entropy of formation of all the ternary oxides from their component binary oxides are relatively small. Although the entropies of formation show some scatter, the average value for Ln = La, Pr, Nd is more negative than the average value for the other lanthanide elements. From this difference, an average value for the structure transformation entropy of Ln(2)O(3) from C-type to A-type is estimated as 0.87 J.mol(-1).K-1. The standard Gibbs energies of formation of these ternary oxides from elements at 1223 K are presented as a function of lanthanide atomic number. By invoking the Neumann-Kopp rule for heat capacity, thermodynamic properties of the inter-oxide compounds at 298.15 K are estimated. (C) 2002 Elsevier Science Ltd. All rights reserved.

System Dy-Fe-O: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

The enthalpy increments and the standard molar Gibbs energies of formation-of DyFeO3(s) and Dy3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent. from the heat capacity data for DyFeO3 at similar to 648 K. A similar type of phase transition has been observed for Dy3Fe5O12 at similar to 560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO3(s) and Dy3Fe5O12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions:{H(0)m(T) - H(0)m(298.15 K)) (Jmol(-1)) (+/-1.1%) = -52754 + 142.9 x (T (K)) + 2.48 x 10(-3) x (T (K))(2) + 2.951 x 10(6) x (T (K))(-1); (298.15 less than or equal to T (K) less than or equal to 1000) for DyFeO3(s), and {H(0)m(T) - H(0)m(298.15 K)} (Jmol(-1)) (+/-1.2%) = -191048 + 545.0 x (T - (K)) + 2.0 x 10(-5) x (T (K))(2) + 8.513 x 10(6) x (T (K))(-1); (208.15 less than or equal to T (K) less than or equal to 1000)for Dy3Fe5O12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO3(s) + Dy2O3(s) + Fe(s)}/YDT/CSZ//{Fe(s) + Fe0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(s)}//CSZ//{DyFeO3(s) + Dy3Fe5O12(s) + Fe3O4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO3 and Dy3Fe5O12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Dy2O3 from the literature, are given by Delta(f)G(0)m(DyFeO3,s)(kJmol(-1))(+/-3.2)= -1339.9 + 0.2473 x (T(K)); (1021 less than or equal to T (K) less than or equal to 1548)and D(f)G(0)m(Dy3Fe5O12,s) (kJmol(-1)) (+/-3.5) = -4850.4 + 0.9846 x (T (K)); (1035 less than or equal to T (K) less than or equal to 1250) The uncertainty estimates for Delta(f)G(0)m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for the system Dy-Fe-O were developed at 1250 K. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Thermodynamic analysis of enzyme catalysed reactions: new insights into the Michaelis-Menten equation

A simple thermodynamic analysis of the well-known Michaelis-Menten equation (MME) of enzyme catalysis is proposed that employs the chemical potential mu to follow the Gibbs free energy changes attending the formation of the enzyme-substrate complex and its turnover to the product. The main conclusion from the above analysis is that low values of the Michaelis constant KM and high values of the turnover number k(cat) are advantageous: this supports a simple algebraic analysis of the MME, although at variance with current thinking. Available data apparently support the above findings. It is argued that transition state stabilisation - rather than substrate distortion or proximity - is the key to enzyme catalysis.

Thermodynamic investigation of the MOCVD of copper films from bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II)

Equilibrium concentrations of various condensed and gaseous phases have been thermodynamically calculated, using the free energy minimization criterion, for the metalorganic chemical vapour deposition (MOCVD) of copper films using bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II) as the precursor material. From among the many chemical species that may possibly result from the CVD process, only those expected on the basis of mass spectrometric analysis and chemical reasoning to be present at equilibrium, under different CVD conditions, are used in the thermodynamic calculations. The study predicts the deposition of pure, carbon-free copper in the inert atmosphere of argon as well as in the reactive hydrogen atmosphere, over a wide range of substrate temperatures and total reactor pressures. Thin films of copper, grown on SiO2/Si(100) substrates from this metalorganic precursor by low pressure CVD have been characterized by XRD and AES. The experimentally determined composition of CVD-grown copper films is in reasonable agreement with that predicted by thermodynamic analysis.

Thermodynamic studies on NdFeO3(s)

The enthalpy increments and the standard molar Gibbs energy of formation of NdFeO3(s) have been measured using a hightemperature Calvet microcalorimeter and a solid oxide galvanic cell, respectively. A lambda-type transition, related to magnetic order-disorder transformation (antiferromagnetic to paramagnetic), is apparent from the heat capacity data at similar to 687 K. Enthalpy increments, except in the vicinity of transition, can be represented by a polynomial expression: {Hdegrees(m)(T)-Hdegrees(m) (298.15 K)} /J(.)mol(-1) (+/- 0.7%)=-53625.6+146.0(T/K) +1.150 X 10(-4)(T/K)(2) +3.007 x 10(6)(T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000). The heat capacity, the first differential of {Hdegrees(m)(T)-Hdegrees(m)(298.15 K)}with respect to temperature, is given by Cdegrees(pm)/J(.)K(-1.)mol(-1)=146.0+ 2.30x10(-4) (T/K) - 3.007 X 10(6)(T/K)(-2). The reversible emf's of the cell, (-) Pt/{NdFeO3(s) +Nd2O3(s)+Fe(s)}//YDT/CSZ// Fe(s)+'FeO'(s)}/Pt(+), were measured in the temperature range from 1004 to 1208 K. It can be represented within experimental error by a linear equation: E/V=(0.1418 +/- 0.0003)-(3.890 +/- 0.023) x 10(-5)(T/K). The Gibbs energy of formation of solid NdFeO, calculated by the least-squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Nd2O3 from the literature, is given by Delta(f)Gdegrees(m)(NdFeO3 s)/kJ (.) mol(-1)( +/- 2.0)=1345.9+0.2542(T/K); (1000 less than or equal to T/K less than or equal to 1650). The error in Delta(f)Gdegrees(m)(NdFeO3, s, T) includes the standard deviation in emf and the uncertainty in the data taken from the literature. Values of Delta(f)Hdegrees(m)(NdFeO3, s, 298.15 K) and Sdegrees(m) (NdFeO3 s, 298.15 K) calculated by the second law method are - 1362.5 (+/-6) kJ (.) mol(-1) and 123.9 (+/-2.5) J (.) K-1 (.) mol(-1), respectively. Based on the thermodynamic information, an oxygen potential diagram for the system Nd-Fe-O was developed at 1350 K. (C) 2002 Elsevier Science (USA).

Two timescale analysis of the Alopex algorithm for optimization

Alopex is a correlation-based gradient-free optimization technique useful in many learning problems. However, there are no analytical results on the asymptotic behavior of this algorithm. This article presents a new version of Alopex that can be analyzed using techniques of two timescale stochastic approximation method. It is shown that the algorithm asymptotically behaves like a gradient-descent method, though it does not need (or estimate) any gradient information. It is also shown, through simulations, that the algorithm is quite effective.

Reliability Based Design Optimization for Internal Stability of Reinforced Soil Structures Using Pseudo‐Static Method

Seismic design of reinforced soil structures involves many uncertainties that arise from the backfill soil properties and tensile strength of the reinforcement which is not addressed in current design guidelines. This paper highlights the significance of variability in the internal stability assessment of reinforced soil structures. Reliability analysis is applied to estimate probability of failure and pseudo‐static approach has been used for the calculation of the tensile strength and length of the reinforcement needed to maintain the internal stability against tension and pullout failures. Logarithmic spiral failure surface has been considered in conjunction with the limit equilibrium method. Two modes of failure namely, tension failure and pullout failure have been considered. The influence of variations of the backfill soil friction angle, the tensile strength of reinforcement, horizontal seismic acceleration on the reliability index against tension failure and pullout failure of reinforced earth structure have been discussed.

A Convex Optimization Framework for Almost Budget Balanced Allocation of a Divisible Good

We address the problem of allocating a single divisible good to a number of agents. The agents have concave valuation functions parameterized by a scalar type. The agents report only the type. The goal is to find allocatively efficient, strategy proof, nearly budget balanced mechanisms within the Groves class. Near budget balance is attained by returning as much of the received payments as rebates to agents. Two performance criteria are of interest: the maximum ratio of budget surplus to efficient surplus, and the expected budget surplus, within the class of linear rebate functions. The goal is to minimize them. Assuming that the valuation functions are known, we show that both problems reduce to convex optimization problems, where the convex constraint sets are characterized by a continuum of half-plane constraints parameterized by the vector of reported types. We then propose a randomized relaxation of these problems by sampling constraints. The relaxed problem is a linear programming problem (LP). We then identify the number of samples needed for ``near-feasibility'' of the relaxed constraint set. Under some conditions on the valuation function, we show that value of the approximate LP is close to the optimal value. Simulation results show significant improvements of our proposed method over the Vickrey-Clarke-Groves (VCG) mechanism without rebates. In the special case of indivisible goods, the mechanisms in this paper fall back to those proposed by Moulin, by Guo and Conitzer, and by Gujar and Narahari, without any need for randomization. Extension of the proposed mechanisms to situations when the valuation functions are not known to the central planner are also discussed. Note to Practitioners-Our results will be useful in all resource allocation problems that involve gathering of information privately held by strategic users, where the utilities are any concave function of the allocations, and where the resource planner is not interested in maximizing revenue, but in efficient sharing of the resource. Such situations arise quite often in fair sharing of internet resources, fair sharing of funds across departments within the same parent organization, auctioning of public goods, etc. We study methods to achieve near budget balance by first collecting payments according to the celebrated VCG mechanism, and then returning as much of the collected money as rebates. Our focus on linear rebate functions allows for easy implementation. The resulting convex optimization problem is solved via relaxation to a randomized linear programming problem, for which several efficient solvers exist. This relaxation is enabled by constraint sampling. Keeping practitioners in mind, we identify the number of samples that assures a desired level of ``near-feasibility'' with the desired confidence level. Our methodology will occasionally require subsidy from outside the system. We however demonstrate via simulation that, if the mechanism is repeated several times over independent instances, then past surplus can support the subsidy requirements. We also extend our results to situations where the strategic users' utility functions are not known to the allocating entity, a common situation in the context of internet users and other problems.