Spin Concentration Research Articles

Characterization of modified low‐density polyethylene by cold atmospheric pressure plasma jet treatment in the melt state

AbstractCold plasma treatment in the melt state is a novel area of research focused on producing modified polymers, hence more research on the underlying plasma‐polymer interactions in this context is needed. In this study, low‐density polyethylene (LDPE) was treated with a cold atmospheric pressure plasma jet (CAPPJ) during melt processing in a polymer batch mixer. Electron spin resonance (ESR) results proved that plasma treatment effectively generates free radicals in the material, increasing the room temperature spin concentration by an order of magnitude to 2 × 1015 spins g−1. The generated radicals react mainly by cross‐linking, forming a gel phase of up to 31%, and consequently increasing the polymer's melt viscosity. Furthermore, oxidation was established as solely a thermal effect limited by radical availability at the interface exposed to the atmosphere, whereas plasma exposure did not lead to further oxidation. Interestingly, plasma appears to interact with the thermally created ketone groups, possibly forming unsaturated carbonyl compounds.

Spin dynamics investigation and structural analysis of ambient scalable Sr2+ doped zirconium ferrite nanoparticles synthesized by low temperature auto combustion route

Microwave spin resonance behaviour of Sr2+ doped Zirconium ferrite Zr1-xSrxFe2O4; (0 ≤ x ≥ 0.20) nanoparticles synthesized by auto combustion route has been investigated by electron paramagnetic resonance (EPR) which show a broad ferromagnetic resonance signal with a superimposed hump signal which is attributed to ferrite Fe3+ ions and oxygen vacancies which is in agreement with XRD and XPS. EPR shows low spin concentration and smaller relaxation time for Zr0.80Sr0.20Fe2O4 which can be used for hyperthermia and for use as a MRI contrast agent. EDS and XPS confirms the presence of Zr, Sr, Fe, O, and C and HRTEM images confirm growth along (220) and (311) with an interatomic distance of 0.3327 nm and 0.2622 nm respectively, thus, authenticating the formation of spinel structure in agreement with FTIR studies. The magnetic behaviour (M − H loop) shows high saturation magnetization and higher value of effective magnetocrystalline anisotropy (Keff) for Zr0.80Sr0.20Fe2O4.

An EPR study of point defects in zinc oxide thin films

We studied ZnO thin films deposited on glass slides by thermal evaporation in vacuum followed by heat treatment in open air or Ar flow. The samples were characterized using x-ray diffraction, Raman scattering, photoluminescence (PL), and electron paramagnetic resonance (EPR) spectroscopy. We observed a broad PL band in the visible region at spectral positions of 504 and 560 nm and a low-intensity band in the UV region at 390 nm. The EPR spectra display a clear first derivative structure at g=1.96 at temperatures below 200 K. The PL spectrum shows red-shifted valence to conduction band emission due to electron hole recombination through shallow surface states. We found an activation energy of E a = 4.2 meV using the Arrhenius plot and estimated concentrations of paramagnetic defects and spin–spin relaxation time constants of 1016 m−3 and 10–14 s, respectively.

Generation and persistency of combustion-derived environmentally persistent free radicals from phenolic compounds over a Fe2O3/SiO2 surface

Combustion of organic solid wastes releases phenolic compounds which can act as precursors in the formation of environmentally persistent free radicals (EPFRs) in the post-flame, cooling zone of waste combustion. The study investigated the generation mechanism of EPFRs from phenolic compounds catalyzed by transition metals in air atmosphere under simulated combustion conditions. Representative combustion-derived phenolic compounds were used, and SiO2 particulates containing different mass ratio of Fe2O3 were synthesized as carriers. EPFRs formed had g-factors between 1.9998 and 2.0066, indicating phenoxyl-, cyclopentadienyl-, and semiquinone-type radicals, along with paramagnetic F-centers. The promotion effect of phenolic compounds on EPFR formation during heating decreased as catechol > hydroquinone > phenol > p-cresol. This trend is related to hydroxyl groups and activation energy. In particular, catechol chemically adsorbed on Fe2O3 at 600 K led to the formation of EPFRs with relatively high spin concentrations (up to 1.28 × 1017 spin/g). Higher Fe2O3 concentrations promoted the transformation of phenoxyl-type radicals into cyclopentadienyl-type and paramagnetic F-centers. However, as the Fe2O3 loading increased from 1.25% to 5%, the density of EPFRs decreased. The findings related to the influence of various precursors and Fe2O3 concentration on EPFR formation provide valuable insights for estimating EPFR generation and associated risk during combustion processes.

Spin and charge interactions between nanographene host and ferrocene.

Ferrocene (FeCp2) was introduced as a non-magnetic guest molecule to activated carbon fibers (ACFs) as a nanographene-based host having localized spins originating from zigzag edges of graphene. The introduction of the guest molecule was confirmed by FTIR for ACFs-FeCp2 introduced at 55 (150) °C (FeCp2-ACFs-55(150)). The appearance of satellite Fe2p peaks and the increase in shake-up peak intensity of the C1s in the XPS spectrum proved the emergence of charge-transfer host-guest interaction in FeCp2-ACFs-150, supported by the red-shift of the G-band in the Raman spectrum. The six-times enhancement in the spin concentration in FeCp2-ACFs-150 compared with ACFs indicates the spin magnetism of the non-magnetic guest FeCp2+ molecule induced by a charge-transfer host-guest interaction in the nanographene host. The larger ESR linewidth than that expected from the dipolar interaction estimated by the localized spin concentration suggests the exchange interaction between the nanographene and FeCp2 spins. The narrowing of the ESR linewidth of FeCp2-ACFs-55 upon higher excitation microwave power suggests the inhomogeneity of the environment for FeCp2+ molecules in the nanographene host. The observed induction of spin magnetism by the interfacial interactions between the nanographene host and the guest molecules will be a promising strategy for developing a new class of molecular magnets.

Re-examination of the intumescence mechanism of ammonium polyphosphate/pentaerythritol/zeolite 4A fire-retarded formulation using advanced spectroscopic techniques

The mixture of ammonium polyphosphate and pentaerythritol is a very efficient intumescent system suitable for polyolefins, especially polypropylene. In this article, the intumescence mechanism of this intumescent system with and without zeolite 4A used as a synergy agent is revisited. The intumescent system was investigated in depth using continuous-wave electron paramagnetic resonance spectroscopy, solid-state nuclear magnetic resonance, and the advanced technique, namely hyperfine sublevel correlation pulsed electron paramagnetic resonance. It was observed that the char generated between 250°C and 350°C is made of polycyclic heterocyclic radicals with nitrogen atoms and that free radicals are mainly generated at these temperatures with a spin concentration relatively stable at least up to 500°C. Moreover, the presence of hydrogen, carbon, nitrogen, and phosphorus was clearly evidenced in the chemical environment of free electrons at 350°C (hyperfine sublevel correlation pulsed electron paramagnetic resonance). Besides, it was also evidenced that 4A totally collapses below 250°C. Contrary to previous works suggesting the presence of aluminosilicophosphate complexes, this work demonstrated that distinct alumino- and silicophosphate complexes are generated and protected the residue at high temperatures.

A novel synthesis from instability difference between SiC 3-C and 6-H crystal to form nanoparticles stems by alkali solution and its degrading various environmental pollutants

In this paper, the nano silicon carbide with different sizes was prepared without hydrofluoric acid by using simple milling and related low temperature etching process in normal pressure. Also, it was the first time verified that 3-C dominated crystalline form of polycrystalline silicon carbide is etched, leaving the 6-H silicon carbide crystalline form by the Raman spectra and HAADF-STEM (high-angle-annular dark-field scanning transmission electron microscopy) imaging that. The application of the alkali etching technique could precise control the partial structural transformation of silicon carbide crystals to a certain extent, which further expands the traditional crystal structure transformation process. In addition, this paper demonstrates the silicon carbide composites in photocatalytic removal of various organic pollutants from aqueous solutions. In the photo degradation of MB (Methylene Blue), the removal rate of the modified silicon carbide shown ten times as much as the commercial silicon carbide. The 1-h degradation efficiency was significantly higher in the 50 μL H2O2 system (100.0%, 86.8% and 89.9% removal of MB, Rhodamine B, Methyl Orange and Tetracycline hydrochloride, respectively). Furthermore, the unit spin concentrations of vacancy defects, superoxide radicals and hydroxyl radicals were quantitatively analyzed. The vacancy defects of the etched material were 1000 times higher than before, and the modified silicon carbide had higher transmittance to infrared and visible light. It strongly absorbs ultraviolet light. Conversely, the research on micron-sized silicon carbide loaded with Ag and Pt atoms found that it had a nitrogen fixation effect during the warming up process, in a nitrogen atmosphere.

Utilizing machine learning to model interdependency of bulk molecular weight, solution concentration, and thickness of spin coated polystyrene thin films

Utilizing machine learning to model interdependency of bulk molecular weight, solution concentration, and thickness of spin coated polystyrene thin films

To What Extent Do Iodomethane and Bromomethane Undergo Analogous Reactions?

Iodomethane and bromomethane (CH3I/CH3Br) are common chemicals, but their chemistry on nanometals is not fully understood. Here, we analyze the reactivity of Rhn+ (n = 3-30) clusters with halomethanes and unveil the spin effect and concentration dependence in the C-H and C-X bond activation. It is found that the reactions under halomethane-rich conditions differ from those under metal-rich conditions. Both CH3I and CH3Br undergo similar dehydrogenation on the Rhn+ clusters in the presence of small quantity reactants; however, different reactions are observed in the presence of sufficient CH3I/CH3Br, showing dominant Rh(CH3Br)x+ (x = 1-4) products but a series of RhnCxHyIz+ species (x = 1-4, y = 1-12, and z = 1-5) pertaining to H2, HI, or CH4 removal. Density functional theory calculations reveal that the dehydrogenation and demethanation of CH3Br are relatively less exothermic and will be deactivated by sufficient gas collisions if helium cooling takes away energy immediately; instead, the successive adsorption of CH3Br gives rise to a series of Rh(CH3Br)x+ species with accidental C-Br bond dissociation.

Pulse Dipolar Electron Paramagnetic Resonance Spectroscopy Distance Measurements at Low Nanomolar Concentrations: The CuII-Trityl Case.

Recent sensitivity enhancements in pulse dipolar electron paramagnetic resonance spectroscopy (PDS) have afforded distance measurements at submicromolar spin concentrations. This development opens the path for new science as more biomolecular systems can be investigated at their respective physiological concentrations. Here, we demonstrate that the combination of orthogonal spin-labeling using CuII ions and trityl yields a >3-fold increase in sensitivity compared to that of the established CuII-nitroxide labeling strategy. Application of the recently developed variable-time relaxation-induced dipolar modulation enhancement (RIDME) method yields a further ∼2.5-fold increase compared to the commonly used constant-time RIDME. This overall increase in sensitivity of almost an order of magnitude makes distance measurements in the range of 3 nm with protein concentrations as low as 10 nM feasible, >2 times lower than the previously reported concentration. We expect that experiments at single-digit nanomolar concentrations are imminent, which have the potential to transform biological PDS applications.

Augmented magnetic nanoparticle assimilation in rGO sheets for tailored static and dynamic magnetic properties in surface functionalized Co0.8Zn0.2Fe2O4 nanoferrite–rGO hybrid structures

This study focuses on the spin dynamics of magnetic rGO nanocomposites, revealing how optimized nanoparticle dispersion influences the spin relaxation time, spin concentration, and magnetic resonance, crucial for advanced magnetic applications.

Optimizing the spin qubit performance of lanthanide-based metal–organic frameworks

Reducing the spin concentration, spin-orbit coupling strength, and ground spin state of lanthanide ions embedded in metal–organic frameworks improves their spin qubit performance.

Novel insights into mass transfer-controlled radical-mediated co-pyrolysis of lignin with typical plastics

Co-pyrolysis of lignin with representative waste plastics, including polypropylene (PP), acrylonitrile butadiene styrene (ABS), polystyrene (PS), and polyethylene terephthalate (PET), was investigated, focusing on radical-mediated reactions, with radical detection via electron paramagnetic resonance (EPR). During the co-pyrolysis of lignin with PP, favorable synergistic effects were observed, resulting in a significant 17 % enhancement in phenolic compound yields within the fixed-bed reactor, whereas the presence of other plastics led to exacerbated cross-linking carbonization in contrast. Furthermore, TOF-MS and FT-ICR-MS analyses corroborated that the bio-oil derived from lignin/PP exhibited a higher phenolic content and lower carbon number distribution. Additionally, the radical concentrations in bio-oil of lignin/PP were determined to be the lowest (1.07 × 1013 spins/µL), providing compelling evidence of the strong interaction between lignin and PP. Interestingly, EPR spectroscopy detected the resultant lowest spin concentrations (1.28 × 1019 spins/g) in lignin/PP char, in contrast to lignin in isolation or within other plastics, which strongly indicating that hydrogen-rich radicals originating from PP were responsible for inducing more effective quenching reactions with lignin intermediates. Moreover, the lignin/PP char demonstrated the highest carbon content (80.30 %) and the lowest ID/IG ratio (1.98), further affirming a highly effective interaction between lignin and PP. The perspective drawn from this study is that the abundant hydrogen source of PP can provide hydrogen-rich radicals to quench lignin intermediates and improve phenolic yield. This intriguing work provides a fresh perspective to evaluate the effect of plastic origin on lignin co-pyrolysis based on radical theory.

Gadolinium Spin Decoherence Mechanisms at High Magnetic Fields.

Favorable relaxation processes, high-field spectral properties, and biological compatibility have made spin-7/2 Gd3+-based spin labels an increasingly popular choice for protein structure studies using high-field electron paramagnetic resonance. However, high-field relaxation and decoherence in ensembles of half-integer high-spin systems, such as Gd3+, remain poorly understood. We report spin-lattice (T1) and phase memory (TM) relaxation times at 8.6 T (240 GHz), and we present the first comprehensive model of high-field, high-spin decoherence accounting for both the electron spin concentration and temperature. The model includes four principal mechanisms driving decoherence: energy-conserving electron spin flip-flops, direct "T1" spin-lattice relaxation-driven electron spin flip processes, indirect T1-driven flips of nearby electron spins, and nuclear spin flip-flops. Mechanistic insight into decoherence can inform the design of experiments making use of Gd3+ as spin probes or relaxivity agents and can be used to measure local average interspin distances as long as 17 nm.

Establishment an integrable model for expansion the application of the electron spin resonance in materials science

Electron spin resonance (ESR) is a highly successful and widely employed characterization and imaging technique within the field of materials science. Consequently, it has found frequent application in materials domain. However, a substantial number of experimental ESR results in this field lack theoretical explanations due to the absence of precise ESR models. To quantitatively analyze ESR results in materials science, this study has developed an asymmetric ESR spectrum model and assessed its efficacy using twenty-two experimental datasets. This model is integrable and capable of estimating spin concentration. Furthermore, this research has sought to establish quantitative associations between key material preparation parameters and the double integral of ESR intensity. This model is poised to enhance the widespread utilization of ESR in materials science.

A nitroxide-containing cathode material for organic radical batteries studied with pulsed EPR spectroscopy

An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times T1 and phase memory times Tm strongly correlate with the ESOC. In the discharged film, the spin concentration reaches 5±3×1020 cm−3, causing a phase memory time Tm≪ 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer Tm between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the ‘bulk’ spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy.

Multiple electron spin resonance echoes observed for paramagnetic defects in diamond at room temperature

Magnetic resonance offers an invaluable testbed for observing and studying the fundamental concepts of quantum cavity interactions with two-level systems in the microwave regime. Typically, these experiments are conducted at low cryogenic temperatures, utilizing spin systems embedded within a high-quality (Q-factor) superconducting cavity. Recent studies indicate that under these conditions, especially in a high-cooperativity regime with strong collective coupling between an electron spin system and a microwave cavity, multiple spin echoes can be detected. These echoes are interpreted as manifestations of coherent quantum effects. To put it simply, photons within the cavity can excite the spin system, which subsequently can stimulate the cavity, creating a feedback loop. In our research, we demonstrate that a specially designed moderate-Q cavity, paired with diamond crystals rich in nitrogen vacancy (NV) centers, allows us to observe such nonlinear quantum phenomena, even at ambient temperatures. Crucially, our experimental design necessitates amplifying the net number of spins for a specific, limited spin concentration. This is achieved by lowering the spins' thermodynamic temperature (as opposed to their physical temperature) to a few kelvins. Notably, we find that maintaining high cooperativity or strong coupling is not essential for these observations. The potential to observe significant microwave cavity quantum effects at room temperature could be useful for future applications, such as quantum memories and quantum sensing.

Ensemble dependence of the critical behavior of a system with long-range interaction and quenched randomness.

We propose a hybrid model governed by the Blume-Emery-Griffiths (BEG) Hamiltonian with a mean-field-like interaction, where the spins are randomly quenched such that some of them are "pure" Ising and the others admit the BEG set of states. It is found, by varying the concentration of the Ising spins, that the model displays different phase portraits in concentration-temperature parameter space, within the canonical and the microcanonical ensembles. Phenomenological indications that these portraits are rich and rather unusual are provided.

Quantitative analyses of the electron spin resonance behavior using an integrable model

Electron spin resonance (ESR) is a spectroscopic method employed to detect distinct species of materials, for example, organic free radicals, transition metal ions, triplet-state molecules, and some point-defect in materials. However, many experimental ESR results of materials have not been theoretically explained due to the lack of a reliable and accurate ESR model. To quantitatively analyze the ESR behavior, we established an asymmetric ESR spectrum model in this study. The effectiveness of this model was confirmed by the results of twenty experimental validations. Because this ESR spectrum model is integrable, spin concentration in materials can be estimated using this model. Furthermore, the quantitative relationships between chemical composition and the double integral of ESR intensity were investigated in this study. The proposed ESR model may expand the application of ESR.

Manipulating solid-state spin concentration through charge transport

Solid-state defects are attractive platforms for quantum sensing and simulation, e.g., in exploring many-body physics and quantum hydrodynamics. However, many interesting properties can be revealed only upon changes in the density of defects, which instead is usually fixed in material systems. Increasing the interaction strength by creating denser defect ensembles also brings more decoherence. Ideally one would like to control the spin concentration at will while keeping fixed decoherence effects. Here, we show that by exploiting charge transport, we can take some steps in this direction, while at the same time characterizing charge transport and its capture by defects. By exploiting the cycling process of ionization and recombination of NV centers in diamond, we pump electrons from the valence band to the conduction band. These charges are then transported to modulate the spin concentration by changing the charge state of material defects. By developing a wide-field imaging setup integrated with a fast single photon detector array, we achieve a direct and efficient characterization of the charge redistribution process by measuring the complete spectrum of the spin bath with micrometer-scale spatial resolution. We demonstrate a two-fold concentration increase of the dominant spin defects while keeping the T2 of the NV center relatively unchanged, which also provides a potential experimental demonstration of the suppression of spin flip-flops via hyperfine interactions. Our work paves the way to studying many-body dynamics with temporally and spatially tunable interaction strengths in hybrid charge-spin systems.