Temperature Dependence Of Time Research Articles

Emergent Research Trends on the Structural Relaxation Dynamics of Molecular Clusters: From Structure-Property Relationship to New Function Prediction.

ConspectusMolecular clusters (MCs) are monodispersed, precisely defined ensembles of atom collections featured with shape-persistent architectures that can deliver certain functions independently. Their molecular compositions and surface functionalities can be tailored feasibly in a predefined manner, and they can be applied as basic structural units to be engineered into materials with desirable hierarchical structures and enriched functions. The chemical systems also offer great opportunities for the design and fabrication of soft structural materials without the chain topologies of polymers. The bulks of MC assemblies demonstrate viscoelasticity that is used to be considered as the unique feature of polymers, while the MC systems are distinct from polymers since their elasticities are resilient even at temperatures 100 K above their glass transition temperatures. The understanding of their anomalous viscoelasticity and the extended studies of general structure-property relationships are desired for the development of new chemical systems for emergent functions and the possibilities to resolve the intrinsic trade-offs of traditional materials.Meanwhile, general macroscopic functions or properties of materials are related to the transportation of mass, momentum, and/or energy, and they are basically realized or directed by the motions of structural units at different length scales. Structural relaxation dynamics research is critical in quantifying motions ranging from fast bond deformation, bond break/formation, and diffusion of ions and particles to the cooperative motions of structure units. Due to the advancement of measurement technology for relaxation dynamics (e.g., quasi-elastic scattering and broadband dielectric spectroscopy), the structural relaxation dynamics of MC materials have been probed for the first time, and their multiple relaxation modes across several temporal scales were systematically studied to bridge the correlation between molecular structures and macroscopic functions. The fingerprint information from dynamics studies, e.g., the temperature dependence of relaxation time and certain property, e.g., ion conductivity, was proposed to quantify the structure-property relationship, and the microscopic mechanism on the mechanical properties, ion conduction, and gas absorption and separation of MC materials can be fully understood.In this Account, to elucidate the uniqueness of MC materials, especially in comparison with polymers, four topics are mainly summarized: structural features, relaxation dynamics characterization techniques, relaxation dynamics characteristics, and quantified understanding of the structure-property relationship. The capability for new function prediction from relaxation dynamics studies is also introduced, and the typical example in impact resistant materials is provided. The Account aims to prove the significance of relaxation dynamics characterization for material innovation, while it also confirms the potential of MCs for functional material fabrications.

Study of molecular interaction between benzaldehyde and methanol using microwave dielectric relaxation spectroscopy and radial distribution function

A microwave dielectric relaxation study was conducted for mixtures of benzaldehyde (BZ) and methanol (MeOH) over a frequency range of 200 MHz to 20 GHz at seven different temperatures, ranging from 293.15 K to 323.15 K. The dielectric relaxation parameters, obtained through a fitting process, were used to examine their dependence on concentration and temperature. Thermodynamic parameters, such as Gibbs free energy (ΔG), molar enthalpy of activation (ΔH), and molar entropy of activation (ΔS), were evaluated using the temperature dependence of the dipolar relaxation time. The study provided valuable insights into the molecular interactions and dynamic behavior of the components in the binary mixture system. Additionally, a molecular dynamics (MD) simulation study was conducted on the binary mixture of BZ and MeOH to determine the Radial Distribution Function (RDF) and coordination number for different pairs of molecules and atoms, which revealed information about the binding and arrangement of the local structure.

Tracking Varroa Parasitism Using Handheld Infrared Cameras: Is Eusocial Fever the Key?

The Varroa destructor is the most significant bee parasite and the greatest threat to bee health all around the world. Due to its hidden lifestyle, detection within the brood cell is only possible through invasive techniques. Enhancing detection methods is essential for advancing research on population dynamics, spread, selection efforts, and control methodologies against the mite. In our study, we employed infrared imaging to measure the thermal differences in parasite and intact Apis mellifera worker broods. Experiments were conducted over two years at the MATE Kaposvár Campus in Hungary involving five beehives in 2022 and five beehives in 2023. A FLIR E5-XT WIFI handheld infrared camera was used to create a heat map of capped brood frames. Our results indicate that the resolution of these cameras is sufficient to provide detailed IR images of a bee colony, making them suitable to detect temperature differences in intact and Varroa parasitized capped brood cells. Mite parasitism causes a time-dependent and sustained temperature increase in developing bee pupae, observable regardless of mite number. Our work demonstrates two different heating patterns: hotspot heating and heating cells that are responsible for the elevated temperature of the Varroa-infested cells as a social fever response by the worker bees. Based on our results, future research combined with AI-based image evaluation software could offer beekeepers and researchers practical and valuable tools for high-throughput, non-invasive Varroa detection in the field.

Thermal response of TBC systems subjected to non-uniform thermal shocks and periodic thermal load: Effect of Biot number and interface imperfection

This study analytically examines the temperature variations within thermal barrier coating (TBC) systems under diverse kinds of thermal loadings, such as concentrated/distributed convective thermal shocks and oscillating thermal loads. In this study, the TBC system comprises ceramic top coat (TC) and NiCrAlY alloy bond coat (BC). The transient behavior of the TBC system facing various kinds of non-uniform convective thermal shocks is elaborated via the dual-phase-lag (DPL) heat conduction model. The effect of imperfect bonding of the TC/BC interface on transient responses of the regions in the neighborhood of the TC/BC interface is studied by considering impermeable, partially permeable and completely permeable heat flux flows. Laplace and Fourier integral transforms are employed to derive the exact solutions of time-dependent temperature fields governing equations. The prominent effects of sudden thermal impulse and steady alternating thermal loading on the variations of temperature within the TC, BC and substrate are inspected. The analysis reveals that the kind of thermal load, loading parameters, thermal properties and thickness of ceramic TC directly affect the transient/periodic temperature fields inside the TBC constituents. Meanwhile, the interface imperfection and the Biot number of convective thermal load play an impressive role in the severity of thermal response of the TBC constituents.

Comparison of two nonlinear formulations of the Maxwell-Cattaneo equation in heat pulse transmission

The nonlinear terms resulting from temperature dependence of thermal conductivity and relaxation time must be considered when studying systems undergoing very short thermal pulses with non-negligible amplitude of the temperature perturbation. Two nonlinear formulations of the Maxwell-Cattaneo-Vernotte equation for thermal transport with relaxation effects are introduced. A comparison of the consequences of these two different nonlinear Cattaneo type equations on thermal pulse propagation is obtained and discussed. The differences in the corresponding velocities and in the corresponding heights of the perturbation peaks turn out to be significant and could be experimentally detected.

A low-cost electronic and optical system for magnetic hyperthermia experimental studies

Magnetic hyperthermia is an alternative to treatments such as chemotherapy and radiotherapy that employs the heat generated by magnetic nanoparticles under the influence of a magnetic field to kill cancer cells while ideally causing no harm to healthy tissues. A low-cost magnetic hyperthermia investigation platform with commercially available and easy-to-assemble parts was presented to provide contribute to and expand research in this area for a larger scientific community. The magnetic hyperthermia measurement system consists of three main parts: a designed thermally insulated sample holder, a commercial 88 kHz magnetic induction heater, and a custom-built fiber optic based refractometer as temperature sensor. The system was tested with commercial EFH-1 magnetic fluids. Time dependent temperature changes were measured for applied magnetic fields of 3.5 kA/m, 4.8 kA/m, and 6.0 kA/m. The corresponding specific loss power values were calculated as 0.28 W/g, 0.51 W/g, and 0.79 W/g, respectively. Intrinsic loss power of commercial ferrofluid is determined as 0.25 ± 0.01 nHm2/kg, found to be comparable to the results of specialized commercial magnetic hyperthermia systems. The results show that the system can easily be used for hyperthermia demonstrations for educational purposes as well as in convenient scientific research with proper calibration.

A quantitative theory for heterogeneous combustion of nonvolatile metal particles in the diffusion-limited regime

The paper presents an analytical theory quantitatively describing the heterogeneous combustion of nonvolatile (metal) particles in the diffusion-limited regime. It is assumed that the particle is suspended in an unconfined, isobaric, quiescent gaseous mixture and the chemisorption of the oxygen takes place evenly on the particle surface. The analytical solution of the particle burn time is derived from the conservation equations of the gas-phase described in a spherical coordinate system with the utilization of constant thermophysical properties, evaluated at a reference film layer. This solution inherently takes the Stefan flow into account. The approximate expression of the time-dependent particle temperature is solved from the conservation of the particle enthalpy by neglecting the higher order terms in the Taylor expansion of the product of the transient particle density and diameter squared. Coupling the solutions for the burn time and time-dependent particle temperature provides quantitative results when initial and boundary conditions are specified. The theory is employed to predict the burn time and temperature of 10–100 μm iron particles, which are then compared with measurements, as the first validation case. The theoretical burn time agrees with the experiments almost perfectly at both low and high oxygen levels. The calculated particle temperature matches the measurements fairly well at relatively low oxygen mole fractions, whereas the theory overpredict the particle peak temperature due to the neglect of evaporation and the possible transition of the combustion regime.Novelty and significance statementFor the first time, we present a comprehensive and quantitative analytical theory elucidating the heterogeneous combustion of nonvolatile (metal) particles in the diffusion-limited regime. This novel theoretical model exhibits a remarkable capacity for quantitative prediction, obviating the need for supplementary information from numerical simulations or experimental data. The derivation process of analytical solutions for burn time and time-dependent particle temperature from conservation equations is elaborated, offering transparency and insight into the model’s foundations. To demonstrate the practical utility of the theory, we apply it to analyze the combustion of iron particles, providing valuable mathematical perspectives on the underlying processes. The model’s predictions for burn time and temperature align closely with experimental results, offering a partial validation of the theory within the realm of its applicable assumptions. This pioneering work contributes a robust and versatile analytical framework, advancing our understanding of diffusion-limited combustion phenomena of nonvolatile particles.

Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence.

The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds [Ln3L3(μ2-F)4(NO3)2](NO3)3. The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ2-F bridges. The detailed analysis of the photophysical properties of the [Eu3L3(μ2-F)4(NO3)2](NO3)3·2H2O and [Tb3L3(μ2-F)4(NO3)2](NO3)3·3H2O complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives. The spectra of mixed species of average composition [Eu1.5Tb1.5L3(μ2-F)4(NO3)2](NO3)3·3H2O are in accordance with the ratiometric luminescent thermometer behavior. Measurements of the direct-current (dc) magnetic susceptibility of the [Dy3L3(μ2-F)4(NO3)2](NO3)3·2H2O complex indicate possible ferromagnetic interactions between the Dy(III) ions. Alternating current (ac) susceptibility measurements of this complex indicate single-molecule magnet behavior in zero dc field with magnetic relaxation dominated by Orbach mechanism and an effective energy barrier Ueff = 12.3 cm-1 (17.7 K) with a pre-exponential relaxation time, τ0 of 7.3 × 10-6 s. A similar reaction of mononuclear macrocyclic complexes with a higher number of fluoride equivalents results in polymeric {[Ln3L3(μ2-F)5](NO3)4}n complexes. The X-ray crystal structure of the Nd(III) derivative of this type shows trinuclear units that are additionally linked by single fluoride bridges to form a linear coordination polymer.

Data Quality in IoT Temperature Sensor Systems: Demonstrated on Time-Dependent Temperature Fluctuations

Data Quality in IoT Temperature Sensor Systems: Demonstrated on Time-Dependent Temperature Fluctuations

Temperature dependence of Fe:ZnSe mid-infrared spectral and laser output properties under ∼4 µm radiation excitation

This paper presents the temperature dependence of the spectroscopic and laser properties of the Fe2+:ZnSe single crystal under excitation by radiation at a wavelength of ∼4.04µm. Excitation was supported by the Er:YAG laser (∼2.94µm) operated in the Q-switched or free-running (FR) mode that pumped the Fe:ZnSe laser cooled by liquid nitrogen to 78 K. This system generated radiation at the wavelength of ∼4.04µm. Temperature dependence of absorption, fluorescence spectra, and fluorescence decay time of Fe2+ ions was measured. The optimal temperature that allows efficient Fe:ZnSe laser system operation with maximum laser output energy was sought in both regimes. It was characterized at a repetition rate of 1 Hz with pulse durations of ∼175ns and ∼155µs in both modes, respectively. The highest laser output energies obtained with the crystal placed in the cryostat in gain-switched (GS) and FR modes were ∼385µJ at 260 K and ∼374µJ at 190 K, respectively. Maximum optical-to-optical efficiencies in the same modes were ∼13% at 260 K and ∼32% at 170 K, respectively. Wide laser radiation oscillation spectra depending on the temperature ranging from ∼4.3µm at 140 K to ∼4.9µm at 340 K obtained with a Gaussian-like beam spatial profile were demonstrated. Under atmospheric conditions at RT, this laser system reached a pulse energy of over 0.5 mJ at ∼4.78µm in ∼135ns pulses, which corresponds to a peak power of ∼3.9kW.

Temperature evolution of laser-ignited micrometric iron particles: A comprehensive experimental data set and numerical assessment of laser heating impact

This study examines the effects of laser heating on the ignition and critical combustion characteristics, such as temperature and burn time, of individual iron particles. It provides time-dependent temperature profiles of laser-ignited particles across a broad spectrum of particle size distributions and oxygen concentrations obtained from experiments, which are a useful database for further development and validation of iron particle combustion models. The herein reported datasets significantly complement those existing in the literature. In the current study, the raw data are thoroughly re-evaluated using refined approaches. For the experimental canonical configuration of single iron particle combustion, an ignition system based on laser heating provides several advantages in overcoming temperature field uncertainties and facilitating controlled environments for optical diagnostics. Despite the inherent uncertainties in laser heating, associated with non-uniform intensity profiles and particle size variations, this study addresses the critical question of how these uncertainties affect in situ measurements of particle temperature and time to reach peak temperature. This study, conducted using a numerical model, reveals a dependence of the particle temperature after laser heating on particle size. However, this dependence does not significantly impact the key parameters of iron-particle combustion, such as the maximum temperature and burn time of the laser-ignited iron particle. The study also presents a comparison between the simulated particle temperature histories and those derived from two-color pyrometry measurements for a wide range of particle size distributions and oxygen concentrations. Notably, by implementing a laser-heating sub-model into an iron particle combustion model, assuming external-diffusion-limited oxidation only up to stoichiometric FeO, the temperature evolution up to the maximum temperature is reasonably captured for a wide range of particle sizes (20–53μm) and oxygen volumetric fractions (14–21vol% O2 mixed with N2). However, with increasing oxygen concentration, the external-diffusion limited model significantly overestimates the heating rate and subsequently the maximum particle temperature.

Non-Debye Behavior of the Néel and Brown Relaxation in Interacting Magnetic Nanoparticle Ensembles.

We used ac-susceptibility measurements to study the superspin relaxation in Fe3O4/Isopar M nanomagnetic fluids of different concentrations. Temperature-resolved data collected at different frequencies, χ″ vs. T|f, reveal magnetic events both below and above the freezing point of the carrier fluid (TF = 197 K): χ″ shows peaks at temperatures Tp1 and Tp2 around 75 K and 225 K, respectively. Below TF, the Néel mechanism is entirely responsible for the superspin relaxation (as the carrier fluid is frozen), and we found that the temperature dependence of the relaxation time, τN(Tp1), is well described by the Dorman-Bessais-Fiorani (DBF) model: τNT=τrexp⁡EB+EadkB T. Above TF, both the internal (Néel) and the Brownian superspin relaxation mechanisms are active. Yet, we found evidence that the effective relaxation times, τeff, corresponding to the Tp2 peaks observed in the denser samples do not follow the typical Debye behavior described by the Rosensweig formula 1τeff=1τN+1τB. First, τeff is 5 × 10-5 s at 225 K, almost three orders of magnitude more that its Néel counterpart, τN~8 × 10-8 s, estimated by extrapolating the above-mentioned DBF analysis. Thus, 1τN≫1τeff, which is clearly not consistent with the Rosensweig formula. Second, the observed temperature dependence of the effective relaxation time, τeff(Tp2), is excellently described by τB-1T=Tγ0exp⁡-E'kBT-T0', a model solely based on the hydrodynamic Brown relaxation, τB(T)=3ηTVHkBT, combined with an activation law for the temperature variation of the viscosity, ηT=η0exp⁡E'/kB(T-T0'. The best fit yields γ0=3ηVHkB = 1.6 × 10-5 s·K, E'/kB = 312 K, and T0' = 178 K. Finally, the higher temperature Tp2 peaks vanish in the more diluted samples (δ ≤ 0.02). This indicates that the formation of larger hydrodynamic particles via aggregation, which is responsible for the observed Brownian relaxation in dense samples, is inhibited by dilution. Our findings, corroborating previous results from Monte Carlo calculations, are important because they might lead to new strategies to synthesize functional magnetic ferrofluids for biomedical applications.

Threshold temperature of superfluorescence generation in CuCl quantum dots under resonant excitation of excitons and resonant two-photon excitation of biexcitons

We studied the threshold temperature of superfluorescence (SF) generation with regard to biexcitons in CuCl quantum dots (QDs) under resonant two-photon excitation of biexcitons and resonant excitation of excitons to demonstrate the influence of initial population densities in the QDs on SF generation. As a result, the threshold temperature under the resonant excitation of excitons was higher than that under the two-photon excitation of biexcitons. This indicates that the high density of excited dots facilitates the rapid establishment of coherence among the dots, overcoming disadvantages of incomplete population inversion and formation process of biexcitons. We performed a theoretical calculation of the time profiles of the biexcitonic emission based on semiconductor luminescence equations. The experimentally obtained temperature dependence of the time profiles was qualitatively reproduced by calculating their dependence on the dephasing rate. In addition, we estimated the temperature dependence of the phase relaxation time of the biexcitons in the CuCl QDs by analyzing the temperature dependence of SF.

Impact of Nickel doping on microstructure and impedance spectroscopy of multiferroic YCrO3

In this work, we study the effect of Ni-doping on the structural and impedance spectroscopy properties of the polycrystalline YCrO3 ceramic sample. The structural analysis shows all the samples crystallize in an orthorhombic structure with the Pnma space group. The depressed and asymmetric semicircle of complex impedance spectra indicates that the relaxation of charge carriers is of non-Debye type, where the thermally activated charge carriers control it. The temperature dependence of relaxation time and electrical conductivity exhibit an anomaly in the vicinity of diffuse-like relaxor transition temperature (TC ∼ 460 K). The analysis of conductivity data shows hopping-type charge conduction. The analysis further indicates that while the dc conductivity increases continuously, the activation energy shows a non-monotonous variation with Ni concentration.

The effect of temperature oscillations on energy storage rectification in harmonic systems

Rectification, the preferential transport of a current in one direction through a system, has garnered significant attention in molecules because of its importance for controlling thermal and electronic currents at the nanoscale. Here, we report the presence of energy storage rectification effects in a molecular chain. This phenomenon is generated by subjecting a harmonic molecular chain to an oscillating temperature gradient and showing that the energy absorption rate of the system depends on the direction of the gradient. We examine how the energy storage rectification ratios in the chain are affected by the oscillating gradient, asymmetry in the chain, and the system parameters. We find that energy storage rectification can be observed in harmonic lattice structures with time-dependent temperatures and that, correspondingly, anharmonicity is not required to generate this rectification mechanism in such systems.

Experimental and numerical simulation studies of electrical resistance of cementitious materials under varying temperature history

Many in-service concrete structures are normally exposed to varying temperature condition. The time-dependent and non-uniform temperature distribution in concrete structures could affect the accurate assessment of their electrical properties. Therefore, the influences of temperature change over time and the spatial variation in temperature on the measured electrical resistance of cementitious materials are still in need of investigation. The coupled thermal-electrical responses of two types of cementitious materials under varying temperature history were investigated by a series of thermal and electrical tests in this study. Then a coupled thermal-electrical finite element (FE) model was developed to simulate the coupled thermal-electrical responses. The results show that the input direct current has a minor effect on the measured electrical resistance by embedded four-probe method and the specimen temperature when it is no greater than 3 mA. The relationship between the measured temperature at 10-mm depth of the specimen and the apparent resistance is well captured by a linear equation. The coupled thermal-electrical finite element model can predict well the developments of specimen temperature and apparent electrical resistance under varying temperature history. The FE results reveal that the non-uniform temperature variation results in the redistribution of electrical current within the tested specimen. However, electrical field between the two inner electrodes is always uniform when the embedded four-probe method is used, which is not affected by the non-uniform temperature variation.

Complex dynamics of partially freezable confined water revealed by combined experimental and computational studies

We investigate water dynamics in mesoporous silica across partial crystallization by combining broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and molecular dynamics simulations (MDS). Exploiting the fact that not only BDS but also NMR field-cycling relaxometry and stimulated-echo experiments provide access to dynamical susceptibilities in broad frequency and temperature ranges, we study both the fully liquid state above the melting point Tm and the dynamics of coexisting water and ice phases below this temperature. It is found that partial crystallization leads to a change in the temperature dependence of rotational correlation times τ, which occurs in addition to previously reported dynamical crossovers of confined water and depends on the pore diameter. Furthermore, we observe that dynamical susceptibilities of water are strongly asymmetric in the fully liquid state, whereas they are much broader and nearly symmetric in the partially frozen state. Finally, water in the nonfreezable interfacial layer below Tm does not exhibit a much debated dynamical crossover at ∼220 K. We argue that its dynamics is governed by a static energy landscape, which results from the interaction with the bordering silica and ice surfaces and features a Gaussian-like barrier distribution. Consistently, our MDS analysis of the motional mechanism reveals a hopping motion of water in thin interfacial layers. The rotational correlation times of the confined ice phases follow Arrhenius laws. While the values of τ depend on the pore diameter, freezable water in various types of confinements and mixtures shows similar activation energies of Ea ≈ 0.43 eV.

Asphalt binder characterization using waveform-based viscoelastic measures and time-temperature superposition principle under large strains

In the United States, currently peak-to-peak oscillatory shear stress-strain data is used in the asphalt binder characterization protocols. This practice necessitates the measurement, usage, and reporting of only peak responses for material characterization and specification even though a sinusoidal waveform is applied. However, in this paper it is argued that with the proliferation of modified binding systems, it is critical to capture and examine the complete waveform data when subjected to both small and large strains. This approach will help properly differentiating between materials. In this study, four modified binders were tested at small and large strain levels while recording the complete response waveform. The recorded waveform data was then used to examine the linear and nonlinear viscoelastic characteristics of these binders. The orthogonal stress decomposition technique was used to delineate elastic and viscous contributions in the nonlinear regime. This study examined the time-temperature dependency under both linear and nonlinear regimes. The time-temperature shift factors obtained from linear regime were effectively applied in the nonlinear regime. Further, all the tested binders showed strain stiffening and shear thinning behavior under most of the testing conditions. This study provides useful insights about the material behavior under nonlinear regime and can serve as a benchmark for further investigation of nonlinear viscoelastic behavior of asphalt binders.

Investigation of the temperature dependence of the dielectric relaxation of chlorobenzene, bromobenzene and iodobenzene

This paper deals with the investigation results of temperature dependence of complex permittivity’sε∗ = έ − iε˝ of chloro, bromo and iodo- benzene at wavelength 11,50 cm and 12,80 cm within the temperature range 20 ÷ -80˚. It is established that dielectric properties of given liquids are characteristic of one relaxation time. The dielectric spectra were studied taking into account other frequencies given in the literature. In all investigated liquids, a jump appears in the real and imaginary parts of the complex permittivity at the point of the phase transition. The temperature dependence of the dielectric relaxation time of molecules in the liquid state has been determined. It was found that with an increase in the amount of the halogen substituent, an increase in the relaxation time occurs. Macroscopic and molecular relaxation times were calculated from the experimental values. The thermodynamic quantities characterizing the process of dielectric relaxation are calculated. The activation enthalpy of dielectric relaxation processes is compared. The studies were carried out using the dielectric spectroscopy method. This method allows a more detailed study of the dielectric properties of the objects of study due to the large equilibrium (“static”) dielectric constant of the object. It has been determined that the height of the potential barrier separating the two equilibrium positions of a polar molecule is greatest in the state of a pure polar liquid and decreases with dilution in a non-polar solvent.

Tuning the Superspin Dynamics in Inverse Spinel Ferrite Nanoparticle Ensembles via Indirect Cation Substitution

We used magnetic and synchrotron X-ray diffraction measurements to investigate the possibility of tuning the strength of magnetic interparticle interactions in nanoparticle ensembles via chemical manipulation. Our main result comes from temperature-resolved in-phase ac-susceptibility data collected on 8 nm average-diameter Ni0.25Zn0.75Fe2O4 (Ni25) and Ni0.5Zn0.5Fe2O4 (Ni50) nanoparticles at different frequencies, χ′ vs. T|f. We found that the relative peak temperature variation per frequency decade, ϕ=∆TT·∆log(f)—a known measure of interparticle interaction strength—exhibits a four-fold increase, from ϕ = 0.04 in Ni50 to ϕ = 0.16 in Ni25. This corresponds to a fundamental change in the nanoparticles’ superspin dynamics, as proven by the fit of phenomenological models to magnetic relaxation data. Indeed, the Ni25 ensemble exhibits superparamagnetic behavior, where the temperature dependence of the superspin relaxation time, τ, is described in the Dorman–Bessais–Fiorani (DBF) model: τT=τrexp⁡EB+EadkBT, with parameters τr = 4 × 10−12 s, and (EB + Ead)/kB = 1473 K. On the other hand, the nanoparticles in the Ni50 ensemble freeze collectively upon cooling in a spin-glass fashion according to a critical dynamics law: τ(T)=τ0TTg−1zν, with τ0 = 4 × 10−8 s, Tg = 145 K, and zν = 7.2. Rietveld refinements against powder X-ray diffraction data reveal the structural details that underlie the observed magnetic behavior: an indirect cation replacement mechanism by which non-magnetic Zn ions are incorporated in the tetrahedral sites of the inverse spinel.