Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 21
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Phys Rev E ; 105(3-1): 034209, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35428131

RESUMO

The concept of dynamical causal effect (DCE) is generalized and equipped with a formalism which allows one to formulate in a unified manner and interrelate a variety of causality quantifiers used in time series analysis. An elementary DCE from a subsystem Y to a subsystem X is defined within the stochastic dynamical systems framework as a response of a future X state to an appropriate variation of an initial (X,Y)-state distribution or a certain parameter of Y or of the coupling element Y→X; this response is quantified in a probabilistic sense via a certain distinction functional; elementary DCEs are assembled over a set of initial variations via an assemblage functional. To include all those aspects, a "triple brackets formula" for the general DCE is suggested and serves as a first principle to produce specific causality quantifiers as realizations of the general DCE. As an application, transfer entropy and Liang-Kleeman information flow are related surprisingly as opposite limit cases in a family of DCEs; it is shown that their "nats per time unit" may differ drastically. The suggested DCE viewpoint links any formal causality quantifier to "intervention-effect" experiments, i.e., future responses to initial variations, and so provides its dynamical interpretation, opening a way to its further physical interpretations in studies of physical systems.

2.
Nanomaterials (Basel) ; 12(2)2022 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-35055249

RESUMO

Fluorinated graphitic layers with good mechanical and chemical stability, polar C-F bonds, and tunable bandgap are attractive for a variety of applications. In this work, we investigated the photolysis of fluorinated graphites with interlayer embedded acetonitrile, which is the simplest representative of the acetonitrile-containing photosensitizing family. The samples were continuously illuminated in situ with high-brightness non-monochromatized synchrotron radiation. Changes in the compositions of the samples were monitored using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS N K-edge spectra showed that acetonitrile dissociates to form HCN and N2 molecules after exposure to the white beam for 2 s, and the latter molecules completely disappear after exposure for 200 s. The original composition of fluorinated matrices CF0.3 and CF0.5 is changed to CF0.10 and GF0.17, respectively. The highly fluorinated layers lose fluorine atoms together with carbon neighbors, creating atomic vacancies. The edges of vacancies are terminated with the nitrogen atoms and form pyridinic and pyrrolic units. Our in situ studies show that the photolysis products of acetonitrile depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials.

3.
Nanomaterials (Basel) ; 11(9)2021 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-34578479

RESUMO

Using a set of microscopic, spectroscopic, and electrochemical methods, a detailed study of the interrelation between the structural and electrochemical properties of the as-prepared nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) and their modified derivatives is carried out. It was found that after treatment of nanotubes with hydrochloric acid, their structure is improved by removing amorphous carbon from the outer layers of N-MWCNTs. On the contrary, ion bombardment leads to the formation of vacancy-type structural defects both on the surface and in the bulk of N-MWCNTs. It is shown that the treated nanotubes have an increased specific capacitance (up to 27 F·g-1) compared to the as-prepared nanotubes (13 F·g-1). This is due to an increase in the redox capacitance. It is associated with the reversible Faraday reactions with the participation of electrochemically active pyridinic and pyrrolic nitrogen inclusions and oxygen-containing functional groups (OCFG). Based on the comparison between cyclic voltammograms of N-MWCNTs treated in HCl and with an ion beam, the peaks on these curves were separated and assigned to specific nitrogen inclusions and OCFGs. It is shown that the rate of redox reactions with the participation of OCFGs is significantly higher than that of reactions with nitrogen inclusions in the pyridinic and pyrrolic forms. Moreover, it was established that treatment of N-MWCNTs in HCl is accompanied by a significant increase in the activity of nitrogen centers, which, in turn, leads to an increase in the rate of redox reactions involving OCFGs. Due to the significant contribution of redox capacitance, the obtained results can be used to develop supercapacitors with increased total specific capacitance.

4.
Chaos ; 31(7): 073127, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-34340361

RESUMO

This work investigates numerics of several widely known phase-dynamic quantifiers of directional (causal) couplings between oscillatory systems: transfer entropy (TE), differential quantifier, and squared-coefficients quantifier based on an evolution map. The study is performed on the system of two stochastic Kuramoto oscillators within the framework of dynamical causal effects. The quantifiers are related to each other and to an asymptotic effect of the coupling on phase diffusion. Several novel findings are listed as follows: (i) for a non-synchronous regime and high enough noise levels, the TE rate multiplied by a certain characteristic time (called here reduced TE) equals twice an asymptotic effect of a directional coupling on phase diffusion; (ii) "information flow" expressed by the TE rate unboundedly rises with the coupling coefficient even in the domain of effective synchronization; (iii) in any effective synchronization regime, the reduced TE is equal to 1/8 n.u. in each direction for equal coupling coefficients and equal noise intensities, and it is in general a simple function of the ratio of noise intensities and the ratio of coupling coefficients.

5.
Nanomaterials (Basel) ; 11(4)2021 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-33916778

RESUMO

In this paper, we propose a facile approach to the management of graphene oxide (GO) chemistry via its synthesis using KMnO4/K2Cr2O7 oxidizing agents at different ratios. Using Fourier Transformed Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and X-ray Absorption Spectroscopy, we show that the number of basal-plane and edge-located oxygenic groups can be controllably tuned by altering the KMnO4/K2Cr2O7 ratio. The linear two-fold reduction in the number of the hydroxyls and epoxides with the simultaneous three-fold rise in the content of carbonyls and carboxyls is indicated upon the transition from KMnO4 to K2Cr2O7 as a predominant oxidizing agent. The effect of the oxidation mixture's composition on the structure of the synthesized GOs is also comprehensively studied by means of X-ray diffraction, Raman spectroscopy, transmission electron microscopy, atomic-force microscopy, optical microscopy, and the laser diffraction method. The nanoscale corrugation of the GO platelets with the increase of the K2Cr2O7 content is signified, whereas the 10-100 µm lateral size, lamellar, and defect-free structure is demonstrated for all of the synthesized GOs regardless of the KMnO4/K2Cr2O7 ratio. The proposed method for the synthesis of GO with the desired chemistry opens up new horizons for the development of graphene-based materials with tunable functional properties.

6.
ACS Omega ; 5(39): 25148-25155, 2020 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-33043193

RESUMO

The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 µm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc.

7.
Materials (Basel) ; 13(19)2020 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-33020425

RESUMO

Vertically aligned carbon nanotube (CNT) arrays show potential for the development of planar low-voltage emission cathodes. The characteristics of cathodes can be improved by modifying their surface, e.g., by hydrogen plasma treatment, as was performed in this work. The surface of multi-walled CNT arrays grown on silicon substrates from toluene and ferrocene using catalytic chemical vapor deposition was treated in a high-pressure (~104 Pa) microwave reactor. The structure, composition, and current-voltage characteristics of the arrays were studied before and after hydrogen plasma treatment at various power values and durations. CNT tips were destroyed and catalytic iron was released from the CNT channels. The etching rate was influenced by iron particles that formed on the array surface. The lower emission threshold in the plasma-treated arrays than in the initial sample is explained by the amplification factor of the local electric field increasing due to graphene structures of unfolded nanotube layers that formed at the CNT tips.

8.
ACS Omega ; 5(18): 10441-10450, 2020 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-32426601

RESUMO

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis.

9.
Sci Rep ; 10(1): 6902, 2020 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-32327708

RESUMO

In this paper we present a facile method for the synthesis of aminated graphene derivative through simultaneous reduction and amination of graphene oxide via two-step liquid phase treatment with hydrobromic acid and ammonia solution in mild conditions. The amination degree of the obtained aminated reduced graphene oxide is of about 4 at.%, whereas C/O ratio is up to 8.8 as determined by means of X-ray photoelectron spectroscopy. The chemical reactivity of the introduced amine groups is further verified by successful test covalent bonding of the obtained aminated graphene with 3-Chlorobenzoyl chloride. The morphological features and electronic properties, namely conductivity, valence band structure and work function are studied as well, illustrating the influence of amine groups on graphene structure and physical properties. Particularly, the increase of the electrical conductivity, reduction of the work function value and tendency to form wrinkled and corrugated graphene layers are observed in the aminated graphene derivative compared to the pristine reduced graphene oxide. As obtained aminated graphene could be used for photovoltaic, biosensing and catalysis application as well as a starting material for further chemical modifications.

10.
Phys Rev E ; 102(6-1): 062139, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33466034

RESUMO

Transfer entropy (TE) is widely used in time-series analysis to detect causal couplings between temporally evolving objects. As a coupling strength quantifier, the TE alone often seems insufficient, raising the question of its further interpretations. Here the TE is related to dynamical causal effects (DCEs) which quantify long-term responses of a coupling recipient to variations in a coupling source or in a coupling itself: Detailed relationships are established for a paradigmatic stochastic dynamical system of bidirectionally coupled linear overdamped oscillators, their practical applications and possible extensions are discussed. It is shown that two widely used versions of the TE (original and infinite-history) can become qualitatively distinct, diverging to different long-term DCEs.

11.
Data Brief ; 25: 104108, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31297418

RESUMO

The data presented in this article are related to the research article entitled "Structure and electrochemical characterization of SnOx/Sn@MWCNT composites formed by pulsed ion beam irradiation" (Korusenko et al., 2019). This article presents the effect of irradiation by pulsed ion beam (PIB) irradiation at various modes on the structure multi-walled carbon nanotubes (MWCNTs) and composites based on MWCNTs and tin oxide as well as cycling performance of these composites. The article also presents the results of the analysis of the structure of the electrodes, obtained on the basis of the initial and irradiated composites.

12.
Chaos ; 28(7): 075303, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30070508

RESUMO

Two quite different types of causal effects are given by (i) changes in near future states of a driven system under changes in a current state of a driving system and (ii) changes in statistical characteristics of a driven system dynamics under changes in coupling parameters, e.g., under switching the coupling off. The former can be called transient causal effects and can be estimated from a time series within the well established framework of the Wiener-Granger causality, while the latter represent equilibrium (or stationary) causal effects which are often most interesting but generally inaccessible to estimation from an observed time series recorded at fixed coupling parameters. In this work, relationships between the two kinds of causal effects are found for unidirectionally coupled stochastic linear oscillators depending on their frequencies and damping factors. Approximate closed-form expressions for these relationships are derived. Their limitations and possible extensions are discussed, and their practical applicability to extracting equilibrium causal effects from time series is argued.

13.
Nanoscale ; 10(27): 13223-13235, 2018 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-29971299

RESUMO

Monodisperse carbon nanodots (MCNDs) having an identical composition, structure, shape and size possess identical chemical and physical properties, making them highly promising for various technical and medical applications. Herein, we report a facile and effective route to obtain monodisperse carbon nanodots 3.5 ± 0.9 nm in size by thermal decomposition of organosilane within the pores of monodisperse mesoporous silica particles with subsequent removal of the silica template. Structural studies demonstrated that the MCNDs we synthesized consist of ∼7-10 defective graphene layers that are misoriented with respect to each other and contain various oxygen-containing functional groups. It was demonstrated that, owing to their identical size and chemical composition, the MCNDs are formed via coagulation primary aggregates ∼10-30 nm in size, which are, in turn, combined into secondary porous spherical aggregates ∼100-200 nm in diameter. The processes of coagulation of MCNDs and peptization of their hierarchical aggregates are fully reversible and can be controlled by varying the MCND concentration or the pH value of the hydrosols. Submicrometer spherical aggregates of MCNDs are not disintegrated as the hydrosol is dried. The thus obtained porous spherical aggregates of MCNDs are promising for drug delivery as a self-disassembling container for medicinal preparations.

14.
Artigo em Inglês | MEDLINE | ID: mdl-26565199

RESUMO

In estimation of causal couplings between observed processes, it is important to characterize coupling roles at various time scales. The widely used Granger causality reflects short-term effects: it shows how strongly perturbations of a current state of one process affect near future states of another process, and it quantifies that via prediction improvement (PI) in autoregressive models. However, it is often more important to evaluate the effects of coupling on long-term statistics, e.g., to find out how strongly the presence of coupling changes the variance of a driven process as compared to an uncoupled case. No general relationships between Granger causality and such long-term effects are known. Here, we pose the problem of relating these two types of coupling characteristics, and we solve it for a class of stochastic systems. Namely, for overdamped linear oscillators, we rigorously derive that the above long-term effect is proportional to the short-term effects, with the proportionality coefficient depending on the prediction interval and relaxation times. We reveal that this coefficient is typically considerably greater than unity so that small normalized PI values may well correspond to quite large long-term effects of coupling. The applicability of the derived relationship to wider classes of systems, its limitations, and its value for further research are discussed. To give a real-world example, we analyze couplings between large-scale climatic processes related to sea surface temperature variations in equatorial Pacific and North Atlantic regions.

15.
Artigo em Inglês | MEDLINE | ID: mdl-25615178

RESUMO

Quantitative characterization of causal couplings from time series is crucial in studies of complex systems of different origin. Various statistical tools for that exist and new ones are still being developed with a tendency to creating a single, universal, model-free quantifier of coupling strength. However, a clear and generally applicable way of interpreting such universal characteristics is lacking. This work suggests a general conceptual framework for causal coupling quantification, which is based on state space models and extends the concepts of virtual interventions and dynamical causal effects. Namely, two basic kinds of interventions (state space and parametric) and effects (orbital or transient and stationary or limit) are introduced, giving four families of coupling characteristics. The framework provides a unifying view of apparently different well-established measures and allows us to introduce new characteristics, always with a definite "intervention-effect" interpretation. It is shown that diverse characteristics cannot be reduced to any single coupling strength quantifier and their interpretation is inevitably model based. The proposed set of dynamical causal effect measures quantifies different aspects of "how the coupling manifests itself in the dynamics," reformulating the very question about the "causal coupling strength."


Assuntos
Modelos Teóricos
16.
Artigo em Inglês | MEDLINE | ID: mdl-23679499

RESUMO

Transfer entropy (TE) seems currently to be the most widely used tool to characterize causal influences in ensembles of complex systems from observed time series. In particular, in an elemental case of two systems, nonzero TEs in both directions are usually interpreted as a sign of a bidirectional coupling. However, one often overlooks that both positive TEs may well be encountered for unidirectionally coupled systems so that a false detection of a causal influence on the basis of a nonzero TE is rather possible. This work highlights typical factors leading to such "spurious couplings": (i) unobserved state variables of the driving system, (ii) low temporal resolution, and (iii) observation errors. All are shown to be particular cases of a general problem: imperfect observations of states of the driving system. Importantly, exact values of TEs, rather than their statistical estimates, are computed here for selected benchmark systems. Conditions for a "spurious" TE to be large and even strongly exceed a "correct" TE are presented and discussed.


Assuntos
Entropia , Modelos Teóricos , Cadeias de Markov
17.
Phys Rev E Stat Nonlin Soft Matter Phys ; 80(1 Pt 2): 016208, 2009 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-19658793

RESUMO

Quantitative characterization of interaction between processes from time series is often required in different fields of natural science including geophysics and biophysics. Typically, one estimates "short-term" influences, e.g., the widely used Granger causality is defined via one-step-ahead predictions. Such an approach does not reveal how strongly the "long-term" behavior of one process under study is affected by the others. To overcome this problem, we introduce the concept of long-term causality, which extends the concept of Granger causality. The long-term causality is estimated from data via empirical modeling and analysis of model dynamics under different conditions. Apart from mathematical examples, we apply both approaches to find out how strongly the global surface temperature (GST) is affected by variations in carbon dioxide atmospheric content, solar activity, and volcanic activity during the last 150 years. Influences of all the three factors on GST are detected with the Granger causality. However, the long-term causality shows that the rise in GST during the last decades can be explained only if the anthropogenic factor (CO2) is taken into account in a model.

18.
Phys Rev E Stat Nonlin Soft Matter Phys ; 79(4 Pt 2): 046204, 2009 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-19518309

RESUMO

The problem of detection and quantitative characterization of directional couplings in an ensemble of noisy oscillators from a time series is addressed. We suggest estimators for the strengths of couplings which are based on modeling the observed oscillations with a set of stochastic phase oscillators and easily interpreted from a physical viewpoint. Moreover, we present an analytic formula for a statistical significance level allowing to reveal an architecture of couplings reliably from a relatively short time series. The technique applies to weakly coupled nonsynchronized oscillators. It is introduced for oscillators with close basic frequencies but can be readily generalized to the case of arbitrary frequencies. Efficiency of the technique is demonstrated in numerical experiments.

19.
Phys Rev E Stat Nonlin Soft Matter Phys ; 71(3 Pt 2A): 036207, 2005 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-15903546

RESUMO

We compare two conceptually different approaches to the detection of weak directional couplings between two oscillatory systems from bivariate time series. The first approach is based on the analysis of the systems' phase dynamics, whereas the other one tests for interdependencies in the reconstructed state spaces of the systems. We analyze the sensitivity of both techniques to weak couplings in numerical experiments by considering couplings between almost identical as well as between significantly different nonlinear systems. We study different degrees of phase diffusion, test the robustness of the two techniques against observational noise, and investigate the influence of the time series length. Our results show that none of the two approaches is generally superior to the other, and we conclude that it is probably the combination of both techniques that would allow the most comprehensive and reliable characterization of coupled systems.

20.
Phys Rev E Stat Nonlin Soft Matter Phys ; 68(4 Pt 2): 046209, 2003 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-14683037

RESUMO

A technique for determination of character and intensity of interaction between the elements of complex systems based on reconstruction of model equations for phase dynamics is extended to the case of short and noisy time series. Corrections, which eliminate systematic errors of the estimates, and expressions for confidence intervals are derived. Analytic results are presented for a particular case of linear uncoupled systems, and their validity for a much wider range of situations is demonstrated with numerical examples. The technique should be useful for the analysis of nonstationary processes in real time, including the situations of significant noise and restrictions on the observation time.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...