58 research outputs found
High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds
We report a first-principles density-functional study of electron-phonon interactions in and thermoelectric transport properties of the full Heusler compounds Sr2BiAu and Sr2SbAu. Our results show that ultrahigh intrinsic bulk thermoelectric performance across a wide range of temperatures is physically possible and point to the presence of multiply degenerate and highly dispersive carrier pockets as the key factor for achieving this. Sr2BiAu, which features ten energy-aligned low-effective-mass pockets (six along Γ-X and four at L), is predicted to deliver n-type zT=0.4-4.9 at T=100-700 K. Comparison with the previously investigated compound Ba2BiAu shows that the additional L pockets in Sr2BiAu significantly increase its low-temperature power factor to a maximum value of 12 mW m-1 K-2 near T=300 K. However, at high temperatures the power factor of Sr2BiAu drops below that of Ba2BiAu because the L states are heavier and subject to strong scattering by phonon deformation, as opposed to the lighter Γ-X states, which are limited by polar-optical scattering. Sr2SbAu is predicted to deliver a lower n-type zT=3.4 at T=750 K due to appreciable misalignment between the L and Γ-X carrier pockets, generally heavier scattering, and a slightly higher lattice thermal conductivity. Soft acoustic modes, which are responsible for the low lattice thermal conductivity, also increase the vibrational entropy and high-temperature stability of these Heusler compounds, suggesting that their experimental synthesis may be feasible. The dominant intrinsic defects are found to be Au vacancies, which drive the Fermi level towards the conduction band and work in favor of n-doping
Using bond-length dependent transferable force constants to predict vibrational entropies in Au-Cu, Au-Pd, and Cu-Pd alloys
A model is tested to rapidly evaluate the vibrational properties of alloys
with site disorder. It is shown that length-dependent transferable force
constants exist, and can be used to accurately predict the vibrational entropy
of substitutionally ordered and disordered structures in Au-Cu, Au-Pd, and
Cu-Pd. For each relevant force constant, a length- dependent function is
determined and fitted to force constants obtained from first-principles
pseudopotential calculations. We show that these transferable force constants
can accurately predict vibrational entropies of L1-ordered and disordered
phases in CuAu, AuPd, PdAu, CuPd, and PdAu. In
addition, we calculate the vibrational entropy difference between
L1-ordered and disordered phases of AuCu and CuPt.Comment: 9 pages, 6 figures, 3 table
The Effect of Lattice Vibrations on Substitutional Alloy Thermodynamics
A longstanding limitation of first-principles calculations of substitutional
alloy phase diagrams is the difficulty to account for lattice vibrations. A
survey of the theoretical and experimental literature seeking to quantify the
impact of lattice vibrations on phase stability indicates that this effect can
be substantial. Typical vibrational entropy differences between phases are of
the order of 0.1 to 0.2 k_B/atom, which is comparable to the typical values of
configurational entropy differences in binary alloys (at most 0.693 k_B/atom).
This paper describes the basic formalism underlying ab initio phase diagram
calculations, along with the generalization required to account for lattice
vibrations. We overview the various techniques allowing the theoretical
calculation and the experimental determination of phonon dispersion curves and
related thermodynamic quantities, such as vibrational entropy or free energy. A
clear picture of the origin of vibrational entropy differences between phases
in an alloy system is presented that goes beyond the traditional bond counting
and volume change arguments. Vibrational entropy change can be attributed to
the changes in chemical bond stiffness associated with the changes in bond
length that take place during a phase transformation. This so-called ``bond
stiffness vs. bond length'' interpretation both summarizes the key phenomenon
driving vibrational entropy changes and provides a practical tool to model
them.Comment: Submitted to Reviews of Modern Physics 44 pages, 6 figure
Pseudopotential study of binding properties of solids within generalized gradient approximations: The role of core-valence exchange-correlation
In ab initio pseudopotential calculations within density-functional theory
the nonlinear exchange-correlation interaction between valence and core
electrons is often treated linearly through the pseudopotential. We discuss the
accuracy and limitations of this approximation regarding a comparison of the
local density approximation (LDA) and generalized gradient approximations
(GGA), which we find to describe core-valence exchange-correlation markedly
different. (1) Evaluating the binding properties of a number of typical solids
we demonstrate that the pseudopotential approach and namely the linearization
of core-valence exchange-correlation are both accurate and limited in the same
way in GGA as in LDA. (2) Examining the practice to carry out GGA calculations
using pseudopotentials derived within LDA we show that the ensuing results
differ significantly from those obtained using pseudopotentials derived within
GGA. As principal source of these differences we identify the distinct behavior
of core-valence exchange-correlation in LDA and GGA which, accordingly,
contributes substantially to the GGA induced changes of calculated binding
properties.Comment: 13 pages, 6 figures, submitted to Phys. Rev. B, other related
publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm
Phonons and related properties of extended systems from density-functional perturbation theory
This article reviews the current status of lattice-dynamical calculations in
crystals, using density-functional perturbation theory, with emphasis on the
plane-wave pseudo-potential method. Several specialized topics are treated,
including the implementation for metals, the calculation of the response to
macroscopic electric fields and their relevance to long wave-length vibrations
in polar materials, the response to strain deformations, and higher-order
responses. The success of this methodology is demonstrated with a number of
applications existing in the literature.Comment: 52 pages, 14 figures, submitted to Review of Modern Physic
Effects of anharmonic strain on phase stability of epitaxial films and superlattices: applications to noble metals
Epitaxial strain energies of epitaxial films and bulk superlattices are
studied via first-principles total energy calculations using the local-density
approximation. Anharmonic effects due to large lattice mismatch, beyond the
reach of the harmonic elasticity theory, are found to be very important in
Cu/Au (lattice mismatch 12%), Cu/Ag (12%) and Ni/Au (15%). We find that
is the elastically soft direction for biaxial expansion of Cu and Ni, but it is
for large biaxial compression of Cu, Ag, and Au. The stability of
superlattices is discussed in terms of the coherency strain and interfacial
energies. We find that in phase-separating systems such as Cu-Ag the
superlattice formation energies decrease with superlattice period, and the
interfacial energy is positive. Superlattices are formed easiest on (001) and
hardest on (111) substrates. For ordering systems, such as Cu-Au and Ag-Au, the
formation energy of superlattices increases with period, and interfacial
energies are negative. These superlattices are formed easiest on (001) or (110)
and hardest on (111) substrates. For Ni-Au we find a hybrid behavior:
superlattices along and like in phase-separating systems, while for
they behave like in ordering systems. Finally, recent experimental
results on epitaxial stabilization of disordered Ni-Au and Cu-Ag alloys,
immiscible in the bulk form, are explained in terms of destabilization of the
phase separated state due to lattice mismatch between the substrate and
constituents.Comment: RevTeX galley format, 16 pages, includes 9 EPS figures, to appear in
Physical Review
Intraperitoneal drain placement and outcomes after elective colorectal surgery: international matched, prospective, cohort study
Despite current guidelines, intraperitoneal drain placement after elective colorectal surgery remains widespread. Drains were not associated with earlier detection of intraperitoneal collections, but were associated with prolonged hospital stay and increased risk of surgical-site infections.Background Many surgeons routinely place intraperitoneal drains after elective colorectal surgery. However, enhanced recovery after surgery guidelines recommend against their routine use owing to a lack of clear clinical benefit. This study aimed to describe international variation in intraperitoneal drain placement and the safety of this practice. Methods COMPASS (COMPlicAted intra-abdominal collectionS after colorectal Surgery) was a prospective, international, cohort study which enrolled consecutive adults undergoing elective colorectal surgery (February to March 2020). The primary outcome was the rate of intraperitoneal drain placement. Secondary outcomes included: rate and time to diagnosis of postoperative intraperitoneal collections; rate of surgical site infections (SSIs); time to discharge; and 30-day major postoperative complications (Clavien-Dindo grade at least III). After propensity score matching, multivariable logistic regression and Cox proportional hazards regression were used to estimate the independent association of the secondary outcomes with drain placement. Results Overall, 1805 patients from 22 countries were included (798 women, 44.2 per cent; median age 67.0 years). The drain insertion rate was 51.9 per cent (937 patients). After matching, drains were not associated with reduced rates (odds ratio (OR) 1.33, 95 per cent c.i. 0.79 to 2.23; P = 0.287) or earlier detection (hazard ratio (HR) 0.87, 0.33 to 2.31; P = 0.780) of collections. Although not associated with worse major postoperative complications (OR 1.09, 0.68 to 1.75; P = 0.709), drains were associated with delayed hospital discharge (HR 0.58, 0.52 to 0.66; P < 0.001) and an increased risk of SSIs (OR 2.47, 1.50 to 4.05; P < 0.001). Conclusion Intraperitoneal drain placement after elective colorectal surgery is not associated with earlier detection of postoperative collections, but prolongs hospital stay and increases SSI risk
A narrative approach exploring philosophy in education and educational research
Published online: 13 Oct 2017.The use of narrative - in this case a fictional dialogue – has been a time-honoured way of exploring ideas and most importantly indispensable for learning, at least since the time of the Sophists. Indeed, the dialogues of Plato exemplify this thesis because the qualities and characteristics of philosophy and philosophising are revealed through their lives. Extending on this premise, we would argue that we learn to understand both the unity and complexity of philosophy – particularly in education and educational research – not by formal philosophical arguments, necessary as they are in some contexts, but by narratives that are relevant, narratives that make the actions of one or more characters intelligible and justifiable. As a result, this article uses a narrative approach for the dual purpose of exhibiting the relevance of philosophy intelligibly exhibited through the examples of the characters put forward (enquiring Ph.D. student and university professor), but at the same time characters we ourselves can learn from as they both dialectically engage with philosophically orientated problems.Steven A. Stolz and Jānis T. Ozoliņ
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