Search Results (5)

We use Co doping to alter the magnetic relaxation dynamics in superparamagnetic nanofluids made of 18 nm average diameter Fe₃O₄ nanoparticles immersed in Isopar M. Ac-susceptibility data recorded at different frequencies and temperatures, χ″vs. T|_f, reveals a major (~100 K) increase in the superspin blocking temperature of the Co_0.2Fe_2.8O₄-based fluid (CFO) compared to its Fe₃O₄ counterpart (FO). We ascribe this behavior to the strengthening of the interparticle magnetic dipole interactions upon Co doping, as demonstrated by the relative χ″-peak temperature variation per frequency decade $\mathsf{\Phi }={\displaystyle \frac{∆\mathrm{T}}{\mathrm{T}·∆\mathrm{l}\mathrm{o}\mathrm{g}\left(\mathrm{f}\right)}}$, which decreases from Φ~0.15 in FO to Φ~0.025 in CFO. In addition, χ″vs. T|_f datasets from the CFO fluid reveal two magnetic events at temperatures T_p1 = 240 K and T_p2 = 275 K, both above the fluid’s freezing point (T_F = 197 K). We demonstrate that the physical rotation of the nanoparticles within the fluid, the Brown mechanism, is entirely responsible for the collective superspin relaxation observed at T_p1, whereas the Néel mechanism, the superspin flip across an energy barrier within the particle, is dominant at T_p2. We confirm this finding through fits of models that describe the temperature dependence of the relaxation time via the two mechanisms: ${\mathsf{\tau }}_{\mathrm{B}}(\mathrm{T})={\displaystyle \frac{3{\mathsf{\eta }}_0{\mathrm{V}}_{\mathrm{H}}}{{\mathrm{k}}_{\mathrm{B}}\mathrm{T}}}\exp \left[{\displaystyle \frac{{\mathrm{E}}^{\prime }}{{\mathrm{k}}_{\mathrm{B}}\left(\mathrm{T}-{{\mathrm{T}}_0}^{\prime }\right)}}\right]$ and ${\mathsf{\tau }}_{\mathrm{N}}\left(\mathrm{T}\right)={\mathsf{\tau }}_0\exp \left[{\displaystyle \frac{{\mathrm{E}}_{\mathrm{B}}}{{\mathrm{k}}_{\mathrm{B}}\left(\mathrm{T}-{\mathrm{T}}_0\right)}}\right]$. The best fits yield ${\mathsf{\gamma }}_0={\displaystyle \frac{3{\mathsf{\eta }}_0{\mathrm{V}}_{\mathrm{H}}}{{\mathrm{k}}_{\mathrm{B}}}}$= 1.5 × 10⁻⁸ s·K, E′/k_B = 7 03 K, and T₀′ = 201 K for the Brown relaxation, and E_B/k_B = 2818 K and T₀ = 143 K for the Néel relaxation. Full article

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 (T_F = 197 K): χ″ shows peaks at temperatures T_p1 and T_p2 around 75 K and 225 K, respectively. Below T_F, 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, τ_N(T_p1), is well described by the Dorman–Bessais–Fiorani (DBF) model: ${\mathsf{\tau }}_N\left(\mathrm{T}\right)={\mathsf{\tau }}_{\mathrm{r}}\exp \left({\displaystyle \frac{{\mathrm{E}}_{\mathrm{B}}+{\mathrm{E}}_{\mathrm{a}\mathrm{d}}}{{\mathrm{k}}_{\mathrm{B}} \mathrm{T}}}\right)$. Above T_F, both the internal (Néel) and the Brownian superspin relaxation mechanisms are active. Yet, we found evidence that the effective relaxation times, τ_eff, corresponding to the T_p2 peaks observed in the denser samples do not follow the typical Debye behavior described by the Rosensweig formula ${\displaystyle \frac{1}{{\tau }_{eff}}}={\displaystyle \frac{1}{{\tau }_N}}+{\displaystyle \frac{1}{{\tau }_B}}$. First, τ_eff is 5 × 10⁻⁵ s at 225 K, almost three orders of magnitude more that its Néel counterpart, τ_N~8 × 10⁻⁸ s, estimated by extrapolating the above-mentioned DBF analysis. Thus, ${\displaystyle \frac{1}{{\tau }_N}}\gg {\displaystyle \frac{1}{{\tau }_{eff}}}$, which is clearly not consistent with the Rosensweig formula. Second, the observed temperature dependence of the effective relaxation time, τ_eff(T_p2), is excellently described by ${\tau }_B^{-1}\left(\mathrm{T}\right)={\displaystyle \frac{T}{{\gamma }_0}}\exp \left[-{\displaystyle \frac{{\mathrm{E}}^{\prime }}{{\mathrm{k}}_{\mathrm{B}}\left(\mathrm{T}-{T_0}^{\prime }\right)}}\right]$, a model solely based on the hydrodynamic Brown relaxation, ${\mathsf{\tau }}_B(\mathrm{T})={\displaystyle \frac{3\eta \left(T\right)V_H}{k_{B}T}}$, combined with an activation law for the temperature variation of the viscosity, $\mathsf{\eta }\left(\mathrm{T}\right)={\mathsf{\eta }}_0\exp \left[E^{\prime }/k_B(T-{T_0}^{\prime }\right]$. The best fit yields ${\gamma }_0={\displaystyle \frac{3\eta V_H}{k_B}}$ = 1.6 × 10⁻⁵ s·K, E′/k_B = 312 K, and T₀′ = 178 K. Finally, the higher temperature T_p2 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. Full article

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 Ni_0.25Zn_0.75Fe₂O₄ (Ni25) and Ni_0.5Zn_0.5Fe₂O₄ (Ni50) nanoparticles at different frequencies, χ′ vs. T|_f. We found that the relative peak temperature variation per frequency decade, $\mathsf{\varphi }=\frac{∆\mathrm{T}}{\mathrm{T}·∆\mathrm{l}\mathrm{o}\mathrm{g}\left(\mathrm{f}\right)}$—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: $\tau \left(\mathrm{T}\right)={\tau }_{\mathrm{r}}\exp \left(\frac{{\mathrm{E}}_{\mathrm{B}}+{\mathrm{E}}_{\mathrm{a}\mathrm{d}}}{{\mathrm{k}}_{\mathrm{B}}\mathrm{T}}\right),$ with parameters τ_r = 4 × 10⁻¹² s, and (E_B + E_ad)/k_B = 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: $\tau (\mathrm{T})=\frac{{\tau }_0}{{\left[\frac{\mathrm{T}}{{\mathrm{T}}_{\mathrm{g}}}-1\right]}^{\mathrm{z}\mathsf{\nu }}}$, with τ₀ = 4 × 10⁻⁸ s, T_g = 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. Full article

We used ac-susceptibility to measure the blocking temperature, T_B, and energy barrier to the magnetization reversal, E_B, of nanomagnetic fluids of different concentrations, c. We collected data on five samples synthesized by dispersing Fe₃O₄ nanoparticles of average diameter ⟨D⟩ = 8 nm in different volumes of carrier fluid (hexane). We found that T_B increases with the increase in c, a behavior predicted by the Dormann–Bessais–Fiorani (DBF) theory. In addition, our observed T_B vs. c dependence is excellently described by a power law T_B = A∙c^γ, with A = 64 K and γ = 0.056. Our data also show that a Néel–Brown activation law $\mathrm{\tau }\left(\mathrm{T}\right)={\mathrm{\tau }}_0\exp \left(\frac{{\mathrm{E}}_{\mathrm{B}}}{{\mathrm{k}}_{\mathrm{B}}\mathrm{T}}\right)$ describes the superspin dynamics in the most diluted sample, whereas an additional energy barrier term, E_ad, is needed at higher concentrations, according to the DBF model: $\mathrm{\tau }\left(\mathrm{T}\right)={\mathrm{\tau }}_{\mathrm{r}}\exp \left(\frac{{\mathrm{E}}_{\mathrm{B}}+{\mathrm{E}}_{\mathrm{a}\mathrm{d}}}{{\mathrm{k}}_{\mathrm{B}}\mathrm{T}}\right).$ We found E_B/k_B = 366 K and additional energy barriers E_ad/k_B that increase linearly with the common logarithm of the volume concentration, from 138 K at c = 8.3 × 10⁻⁴% to 745 K at c = 4 × 10⁻²%. These results add to our understanding of the contributions by different factors to the superspin dynamics. In addition, the quantitative relations that we established between the T_B, E_ad, and c support the current efforts towards the rational design of functional nanomaterials. Full article

We used dc magnetization and ac susceptibility to investigate the magnetic relaxation of ferrofluids made of 8 nm average-diameter Fe₃O₄ nanoparticles dispersed in hexane. Samples of different concentrations (δ) spanning two orders of magnitude ranging from 0.66 to 0.005 mg (Fe₃O₄)/mL (hexane) were used to vary the interparticle interaction strength. Our data reveal a critical concentration, δ_c = 0.02 mg/mL, below which the ferrofluid behaves like an ideal nanoparticle ensemble where the superspins relax individually according to a Néel–Brown activation law $\mathsf{\tau }(\mathrm{T})={\mathsf{\tau }}_0\exp \left(\frac{{\mathrm{E}}_{\mathrm{B}}}{{\mathrm{k}}_{\mathrm{B}}\mathrm{T}}\right)$ with a characteristic time τ_o ~10⁻⁹ s. That is further confirmed by the observed invariance of the relative peak temperature variation per frequency decade $∆=\frac{∆\mathrm{T}}{\mathrm{T}·∆\mathrm{l}\mathrm{o}\mathrm{g}\left(\mathrm{f}\right)}$, which stays constant at ~0.185 when δ < δ_c. At higher concentrations, between 0.02 and 0.66 mg/mL, we found that Δ exhibits a monotonic increase with the inverse concentration, $\frac{1}{\delta }$, and the collective superspin dynamics is described by a Vogel–Fulcher law, $\mathsf{\tau }(\mathrm{T})={\mathsf{\tau }}_0\exp \left[\frac{{\mathrm{E}}_{\mathrm{B}}}{{\mathrm{k}}_{\mathrm{B}}\left(\mathrm{T}-{\mathrm{T}}_0\right)}\right]$. Within this regime, the dipolar interaction strength parameter T₀ increases from T₀ = 0 K at δ_c = 0.02 mg/mL to T₀ = 14.7 K at δ = 0.66 mg/mL. Full article