1,812 research outputs found
Low temperature superlattice in monoclinic PZT
TEM has shown that the strongly piezoelectric material Pb(Zr0.52Ti0.48)O3
separates into two phases at low temperatures. The majority phase is the
monoclinic phase previously found by x-ray diffraction. The minority phase,
with a nanoscale coherence length, is a slightly distorted variant of the first
resulting from the anti-phase rotation of the oxygen octahedra about [111].
This work clears up a recent controversy about the origin of superlattice peaks
in these materials, and supports recent theoretical results predicting the
coexistence of ferroelectric and rotational instabilities.Comment: REVTeX4, 4 eps figures embedded. JPG version of figs. 2&4 is also
include
Stability of the monoclinic phase in the ferroelectric perovskite PbZr(1-x)TixO3
Recent structural studies of ferroelectric PbZr(1-x)TixO3 (PZT) with x= 0.48,
have revealed a new monoclinic phase in the vicinity of the morphotropic phase
boundary (MPB), previously regarded as the the boundary separating the
rhombohedral and tetragonal regions of the PZT phase diagram. In the present
paper, the stability region of all three phases has been established from high
resolution synchrotron x-ray powder diffraction measurements on a series of
highly homogeneous samples with 0.42 <=x<= 0.52. At 20K the monoclinic phase is
stable in the range 0.46 <=x<= 0.51, and this range narrows as the temperature
is increased. A first-order phase transition from tetragonal to rhombohedral
symmetry is observed only for x= 0.45. The MPB, therefore, corresponds not to
the tetragonal-rhombohedral phase boundary, but instead to the boundary between
the tetragonal and monoclinic phases for 0.46 <=x<= 0.51. This result provides
important insight into the close relationship between the monoclinic phase and
the striking piezoelectric properties of PZT; in particular, investigations of
poled samples have shown that the monoclinic distortion is the origin of the
unusually high piezoelectric response of PZT.Comment: REVTeX file, 7 figures embedde
Phase diagram of the ferroelectric-relaxor (1-x)PbMg(1/3)Nb(2/3)O3-xPbTiO3
Synchrotron x-ray powder diffraction measurements have been performed on
unpoled ceramic samples of (1-x)PbMg(1/3)Nb(2/3)O3-xPbTiO3 (PMN-xPT) with 30%<=
x<= 39% as a function of temperature around the morphotropic phase boundary
(MPB), which is the line separating the rhombohedral and tetragonal phases in
the phase diagram. The experiments have revealed very interesting features
previously unknown in this or related systems. The sharp and well-defined
diffraction profiles observed at high and intermediate temperatures in the
cubic and tetragonal phases, respectively, are in contrast to the broad
features encountered at low temperatures. These peculiar characteristics, which
are associated with the monoclinic phase of MC-type previously reported by Kiat
et al and Singh et al., can only be interpreted as multiple coexisting
structures with MC as the major component. An analysis of the diffraction
profiles has allowed us to properly characterize the PMN-xPT phase diagram and
to determine the stability region of the monoclinic phase, which extends from
x= 31% to x= 37% at 20 K. The complex lansdcape of observed phases points to an
energy balance between the different PMN-xPT phases which is intrinsically much
more delicate than that of related systems such as PbZr(1-x)TixO3 or
(1-x)PbZn(1/3)Nb(1/3)O3-xPbTiO3. These observations are in good accord with an
optical study of x= 33% by Xu et al., who observed monoclinic domains with
several different polar directions coexisting with rhombohedral domains, in the
same single crystal.Comment: REVTeX4, 11 pages, 10 figures embedde
Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: Laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA)
Solid-state voltammetric (micro)electrodes have been used in a variety of environments to study biogeochemical processes. Here we show the wealth of information that has been obtained in the study of sediments, microbial mats, cultures and the water column including hydrothermal vents. Voltammetric analyzers have been developed to function with operator guidance and in unattended mode for temporal studies with an in situ electrochemical analyzer (ISEA). The electrodes can detect the presence (or absence) of a host of redox species and trace metals simultaneously. The multi-species capacity of the voltammetric electrode can be used to examine complex heterogeneous environments such as the root zone of salt marsh sediments. The data obtained with these systems clearly show that O2 and Mn2+ profiles in marine sedimentary porewaters and in microbial biofilms on metal surfaces rarely overlap indicating that O2 is not a direct oxidant for Mn2+. This lack of overlap was suggested originally by Joris Gieskes\u27 group. In waters emanating from hydrothermal vents, Fe2+, H2S and soluble molecular FeS clusters (FeSaq) are detected indicating that the reactants for the pyrite formation reaction are H2S and soluble molecular FeS clusters. Using the ISEA with electrodes at fixed positions, data collected continuously over three days near a Riftia pachyptila tubeworm field generally show that O2 and H2S anti-correlate and that H2S and temperature generally correlate. Unlike sedimentary environments, the data clearly show that Riftia live in areas where both O2 and H2S co-exist so that its endosymbiont bacteria can perform chemosynthesis. However, physical mixing of diffuse flow vent waters with oceanic bottom waters above or to the side of the tubeworm field can dampen these correlations or even reverse them. Voltammetry is a powerful technique because it provides chemical speciation data (e.g.; oxidation state and different elemental compounds/ions) as well as quantitative data. Because (micro)organisms occupy environmental niches due to the system\u27s chemistry, it is necessary to know chemical speciation. Voltammetric methods allow us to study how chemistry drives biology and how biology can affect chemistry for its own benefit
High pressure phases in highly piezoelectric Pb(Zr0.52Ti0.48)O3
Two novel room-temperature phase transitions are observed, via synchrotron
x-ray diffraction and Raman spectroscopy, in the Pb(Zr0.52Ti0.48)O3 alloy under
hydrostatic pressures up to 16 GPa. A monoclinic (M)-to-rhombohedral (R1) phase
transition takes place around 2-3 GPa, while this R1 phase transforms into
another rhombohedral phase, R2, at about 6-7 GPa. First-principles calculations
assign the R3m and R3c symmetry to R1 and R2, respectively, and reveal that R2
acts as a pressure-induced structural bridge between the polar R3m and a
predicted antiferrodistortive R-3c phase.Comment: REVTeX, 4 pages with 3 figures embedded. Figs 1 and 3 in colo
A tetragonal-to-monoclinic phase transition in a ferroelectric perovskite: the structure of PbZr(0.52)Ti(0.48)O3
The perovskite-like ferroelectric system PbZr(1-x)Ti(x)O3 (PZT) has a nearly
vertical morphotropic phase boundary (MPB) around x=0.45-0.50. Recent
synchrotron x-ray powder diffraction measurements by Noheda et al. [Appl. Phys.
Lett. 74, 2059 (1999)] have revealed a new monoclinic phase between the
previously-established tetragonal and rhombohedral regions. In the present work
we describe a Rietveld analysis of the detailed structure of the tetragonal and
monoclinic PZT phases on a sample with x= 0.48 for which the lattice parameters
are respectively: at= 4.044 A, ct= 4.138 A, at 325 K, and am= 5.721 A, bm=
5.708 A, cm= 4.138 A, beta= 90.496 deg., at 20K. In the tetragonal phase the
shifts of the atoms along the polar [001] direction are similar to those in
PbTiO3 but the refinement indicates that there are, in addition, local
disordered shifts of the Pb atoms of ~0.2 A perpendicular to the polar axis..
The monoclinic structure can be viewed as a condensation along one of the
directions of the local displacements present in the tetragonal phase. It
equally well corresponds to a freezing-out of the local displacements along one
of the directions recently reported by Corker et al.[J. Phys. Condens.
Matter 10, 6251 (1998)] for rhombohedral PZT. The monoclinic structure
therefore provides a microscopic picture of the MPB region in which one of the
"locally" monoclinic phases in the "average" rhombohedral or tetragonal
structures freezes out, and thus represents a bridge between these two phases.Comment: REVTeX, 7 figures. Modifications after referee's suggestion: new
figure (figure 5), comments in 2nd para. (Sect.III) and in 2nd & 3rd para.
(Sect. IV-a), in the abstract: "...of ~0.2 A perpendicular to the polar
axis.
Atomic-scale surface demixing in a eutectic liquid BiSn alloy
Resonant x-ray reflectivity of the surface of the liquid phase of the
BiSn eutectic alloy reveals atomic-scale demixing extending over
three near-surface atomic layers. Due to the absence of underlying atomic
lattice which typically defines adsorption in crystalline alloys, studies of
adsorption in liquid alloys provide unique insight on interatomic interactions
at the surface. The observed composition modulation could be accounted for
quantitatively by the Defay-Prigogine and Strohl-King multilayer extensions of
the single-layer Gibbs model, revealing a near-surface domination of the
attractive Bi-Sn interaction over the entropy.Comment: 4 pages (two-column), 3 figures, 1 table; Added a figure, updated
references, discussion; accepted at Phys. Rev. Let
Redox Couples of Inducible Nitric Oxide Synthase
We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals Fe^(III/II) and Fe^(II/I) couples at −191 and −1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the Fe^(III/II) potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of Fe^(III) reduction. Voltammetry at higher scan rates (with pH variations) reveals that the Fe^(III/II) cathodic peak can be resolved into two components, which are attributable to Fe^(III/II) couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS
THERMAL DENATURATION OF MONOMERIC AND TRIMERIC PHYCOCYANINS STUDIED BY STATIC AND SPECTROSCOPY POLARIZED TIME-RESOLVED FLUORESCENCE
C-Phycocyanin (PC) and allophycocyanin (APC). as well as the a-subunit of PC. have been
isolated from the blue-green alga (cyanobacterium). Spirulina platensis. The effects of partial thermal
denaturation of PC and of its state of aggregation have been studied by ps time-resolved, polarized
fluorescence spectroscopy. All measurements have been performed under low photon fluxes (< 10’ ’
photonsipulse x cm’) to minimize singlet-singlet annihilation processes. A complex decay is obtained
under most conditions, which can be fitted satisfactorily with a bi-exponential (7’ = 70400 ps. T? =
1000-3000 ps) for both the isotropic and the polarized part, but with different intensities and time
constants for the two decay curves. The data are interpreted in the frameworkof the model first developed
by Teak and Dale (Biochern. J. 116, 161 (1970)], which divides the spectroscopically different
chromophores in (predominantly) sensitizing (s) and fluorescing U, ones. If one assumes temperature
dependent losses in the energy transfer from the s to the f and between f chromophores. both the
biexponential nature of the isotropic fluorescence decay and the polarization data can be rationalized. In
the isotropic emission (corresponding to the population of excited states) the short lifetime is related to the
s-,f transfer. the longer one to the “free“ decay of the final acceptor(s) (= f). The polarized part is
dominated by an extremely short decay time. which is related to s+f transfer, as well as to resonance
transfer between the f-chromophores
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