107 research outputs found
Segmental Dynamics of Entangled Poly(ethylene oxide) Melts: Deviations from the Tube-Reptation Model
© 2018 American Chemical Society. The dynamics of entangled polymer melts not only is of fundamental theoretical interest but also has wide-reaching consequences for developing a theoretical foundation for investigating biological macromolecules and complex systems relevant to material sciences. Despite several decades of intensive experimental and theoretical research in this field, open questions remain regarding segmental dynamics over the wide range of time scales from local to global motion. This work employs a novel approach based on nuclear magnetic relaxation to scrutinize the character of dipolar interactions in entangled polymer melts, thereby accessing unique information about segmental diffusion and rotation. The main focus is set on the separate consideration of intra- and intermolecular contributions to the proton dipolar interactions, which have been previously shown to possess a different, nontrivial time dependence. A combination of well-established field-cycling T1 relaxometry and recently developed methods based on spin echo is utilized to investigate dipolar couplings in entangled poly(ethylene oxide) melts of various molecular weights. Isolation of the intermolecular contributions to the corresponding experimental quantities provides a means to observe segmental translations taking place during more than 6 orders of magnitude in time. Time dependences of the mean-square displacement obtained in this way revealed apparent exponents of the power laws significantly deviating from predictions of the widely used tube-reptation model of polymer dynamics in the regime of entangled motion. In addition to that, the relative ratio of intermolecular dipolar interactions over the intramolecular counterpart is probed through their corresponding contributions to the transverse relaxation rate. A strong deviation from the tube-reptation model predictions for the evolution of this quantity is observed in the whole range probed experimentally. The obtained data do not reflect the restricted character of segmental motion anticipated in the corresponding time regime. It is emphasized that similar results, both in amplitude and in qualitative behavior, have been previously demonstrated in polybutadiene and polyethylene-alt-propylene, thereby allowing to discuss the universality of the observed deviation
Detection and modeling of hole capture by single point defects under variable electric fields
Understanding carrier trapping in solids has proven key to semiconductor
technologies but observations thus far have relied on ensembles of point
defects, where the impact of neighboring traps or carrier screening is often
important. Here, we investigate the capture of photo-generated holes by an
individual negatively-charged nitrogen-vacancy (NV) center in diamond at room
temperature. Using an externally gated potential to minimize space-charge
effects, we find the capture probability under electric fields of variable sign
and amplitude shows an asymmetric-bell-shaped response with maximum at zero
voltage. To interpret these observations, we run semi-classical Monte Carlo
simulations modeling carrier trapping through a cascade process of phonon
emission, and obtain electric-field-dependent capture probabilities in good
agreement with experiment. Since the mechanisms at play are insensitive to the
trap characteristics, the capture cross sections we observe - largely exceeding
those derived from ensemble measurements - should also be present in materials
platforms other than diamond
Dynamic-nuclear-polarization-weighted spectroscopy of multi-spin electronic-nuclear clusters
Nuclear spins and paramagnetic centers in a solid randomly group to form
clusters featuring nearly-degenerate, hybrid states whose dynamics are central
to processes involving nuclear spin-lattice relaxation and diffusion. Their
characterization, however, has proven notoriously difficult mostly due to their
relative isolation and comparatively low concentration. Here, we combine
field-cycling experiments, optical spin pumping, and variable radio-frequency
(RF) excitation to probe transitions between hybrid multi-spin states formed by
strongly coupled electronic and nuclear spins in diamond. Leveraging bulk
nuclei as a collective time-integrating sensor, we probe the response of these
spin clusters as we simultaneously vary the applied magnetic field and RF
excitation to reconstruct multi-dimensional spectra. We uncover complex nuclear
polarization patterns of alternating sign that we qualitatively capture through
analytical and numerical modeling. Our results unambiguously expose the impact
that strongly-hyperfine-coupled nuclei can have on the spin dynamics of the
crystal, and inform future routes to spin cluster control and detection
Study of correlation of oil flow properties with nuclear magnetic resonance and self-diffusion characteristics
© Copyright 2016.Correlation curves of viscosity, average spin-spin relaxation time, and average self-diffusion for crude oil samples from Tatarstan oil fields have been obtained. Two different averaging models were used to calculate mean values. It has been found that self-diffusion D and average spin-spin relaxation time R2 are best correlated in case reciprocal values 1/R and 1/D are averaged
Structural and chemical embrittlement of grain boundaries by impurities: a general theory and first principles calculations for copper
First principles calculations of the Sigma 5 (310)[001] symmetric tilt grain
boundary in Cu with Bi, Na, and Ag substitutional impurities provide evidence
that in the phenomenon of Bi embrittlement of Cu grain boundaries electronic
effects do not play a major role; on the contrary, the embrittlement is mostly
a structural or "size" effect. Na is predicted to be nearly as good an
embrittler as Bi, whereas Ag does not embrittle the boundary in agreement with
experiment. While we reject the prevailing view that "electronic" effects
(i.e., charge transfer) are responsible for embrittlement, we do not exclude
the role of chemistry. However numerical results show a striking equivalence
between the alkali metal Na and the semi metal Bi, small differences being
accounted for by their contrasting "size" and "softness" (defined here). In
order to separate structural and chemical effects unambiguously if not
uniquely, we model the embrittlement process by taking the system of grain
boundary and free surfaces through a sequence of precisely defined gedanken
processes; each of these representing a putative mechanism. We thereby identify
three mechanisms of embrittlement by substitutional impurities, two of which
survive in the case of embrittlement or cohesion enhancement by interstitials.
Two of the three are purely structural and the third contains both structural
and chemical elements that by their very nature cannot be further unravelled.
We are able to take the systems we study through each of these stages by
explicit computer simulations and assess the contribution of each to the nett
reduction in intergranular cohesion. The conclusion we reach is that
embrittlement by both Bi and Na is almost exclusively structural in origin;
that is, the embrittlement is a size effect.Comment: 13 pages, 5 figures; Accepted in Phys. Rev.
Communication: Proton NMR dipolar-correlation effect as a method for investigating segmental diffusion in polymer melts
© 2016 Author(s).A simple and fast method for the investigation of segmental diffusion in high molar mass polymer melts is presented. The method is based on a special function, called proton dipolar-correlation build-up function, which is constructed from Hahn Echo signals measured at times t and t/2. The initial rise of this function contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean squared displacements (MSDs) of polymer segments from different macromolecules, while the intramolecular part reflects segmental reorientations. Separation of both contributions via isotope dilution provides access to segmental displacements in polymer melts at millisecond range, which is hardly accessible by other methods. The feasibility of the method is illustrated by investigating protonated and deuterated polybutadiene melts with molecular mass 196 000 g/mol at different temperatures. The observed exponent of the power law of the segmental MSD is close to 0.32 ± 0.03 at times when the root MSD is in between 45 Å and 75 Å, and the intermolecular proton dipole-dipole contribution to the total proton Hahn Echo NMR signal is larger than 50% and increases with time
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