Brownian particle-kinetics in a superparamagnetic ferrofluid subjected to static magnetic-field Suko Bagus Trisnanto! and Yoshitaka Kitamoto'” ‘Department of Innovative and Engineered Materials, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku Yokohama, 226-8502, Japan. * Corresponding author: kitamoto y.aa@muitech.2c.jp Abstract, The stochastic Brownian particle-kinetics in a supesparamagnetic ferrofluid at room temperatu significance in nullifying total magnetization vectors of the suspended particles. Correspondingly ‘magnetization response observed under staie magnetic field shows no hysteresis loop, but ; ft field-diference. Owing to this superparamagnetism, we propose a differential magnetometry to analyze the static eld induced particle-kneis and further to idenify the effective fieldstrengh in feonenting paticl-moments toward the Applied field direction. A polydispersive ferroflud containing iron-oxide nanoparticles, in practice, is subjected to a very~ tow oscillatory-feld, immediately aller applying the statie-field For 2 given fequency, we confirm a deereasing as suscepibility a8 de fel-strength increases, which suggests a statistically less Muctuating magnetiation-vectos, Via ‘numerical integration of ae susceptibility recorded, we furthermore estimate the nonlinear quasi-static magnetization i ‘arious measurement frequencies. The resulting nonlinearity is attnbutable tothe contributing relaxation dynamics ofthe particles. More importantly, the difference between dc and ac susceptibilities is found to be fied-strength and frequency dependent. Its value is further maximized at an effective field-strength, from which we identified the coexisting ene bariers the apparent being linear at a given finite IN RODUCTION “ionalizing magnetic ndnoparticles. For instance, the superparamagnetic nanostructures have been contributing to developing many nanotechnological applications particularly aimed for therapeutics, diagnostics or their combination (i.e. theranostics) {1-3). Furthermore, many recent reports indicate that such cell ting (4, $} and imaging [6, 7), as well as biosensing [8] which utilize magnetic nanoparticles as their promoting agents, are no longer theoretical assessments, but an applicable concept, Toward optimizing the pe of these liquid-based biomedical applications, a fundamental study concerning the origin of superparamagnetism in a colloidal nanoparticle system is thus of importance. Nevertheless, behavior under an extemal static magneti is not well-established in terms of understanding panicle field. The most acceptable theory argues that superparamagnetism is ‘none but the resulting thermodynamic behavior of single-domain ferromagnetic nanoparticles, in which thermal agitation is responsible for kinetically and thermally randomizing each magnetization vector of the particles suspended ina viscous medium [9]. As no spontaneous magnetization is observable at room temperature, superparamagnetic ferrofluid, by default, demonstrates no hysteresis loop but a high saturation value in its static ‘magnetization response How magnetic nanoparticles behave under a given magnetic field is experimentally recognizable from their relaxation responses of dynamic magnetization, which are generally classified as physical (Brownian) relaxation {10} and moment (Néel) relaxation (11) {For cach relaxation mechanism, a charactenstic relaxation time-constant exists to define the phase-difference Py ie resulting magnetization arMagNeTM OF a CONOR anOparicle system, however, cludes both relaxation phetomeca by The iags Conference 2018 AIP Goel Proc 1897 Sona fos Pubtaded y AIP Painting 020021-1 trons aera poea AH dt ould wnke strc dy Ha Belaxation behav’ oun P wrelicles: intucing an effective relavation-tine to which the spectal response of dynamic magne [12], Through characterizing ficld-dependent relaxation bel offers a new approach in distinguishing the physical p from the thermal moment relaxation. ion is very sensitive ior of @ superparamagnetic ferrofluid, this article article relaxation under the static mag c-field, selectively METHODOLOGY Displaying a nonlinear Langevin curve of ma \gnetization versus static maunetic-field, fc superparamagnetism ‘has an approwimately linear characteristics for a given finite ficld-difference ¥Thus, a smalf Mucn Tin the spread TET Aw pOPORTATATTY TSTUTE Tie Sate home mae by a nfoMent-dilte SEU AT GRMN emai Be Mo inlentionally set to havea sullicientiy-low a AH should have ficant.contribulion in magnetizing the ample, but a strong correlation to ‘FelaNation behavior of the suspended particles, Owing to thi Principle, we propose a dilferential maunclonictry which Tnitally measures the frequency-dependent complex susceptibility duc to lo amplitude ac-field, for a given Se-field with a finite increment AH: both ac and de fields are parallel. We, Then numerically integrate Am/AH over ‘SMe for estimating ma, as Mustrated in Fig Tay To Theaeee the nonlinear magnetization at low field-regime (Le. finite superparamagnetism) of the polydispersive ferrofluid samples, for representative demonstration, we measured the complex susceptibility by applying 2 Ocr at 0Hz.t9 100 kLlz under an increasing static field from 0 (o 00 Oe. Maateally Bins Rea sae ek a hl strength (far ab 0 magnetic ‘SGOT Hoigy, which are the lits ofthis method Neveticles a rehiivey Tow felstenyth should be powctle STSAUTATE The magnetization of a ferromagnetic nanoparticle, with regard tothe particle size, e) 47.2 mg Fein 80 4! water 101 10 Ft) 1g 75 Mye(Oe) 295 (2) Difetetial magnctomety, in principe, relies on the linearity of magnetization response at finite field-diference, can be upprosimated fom (b) the fequency-dependenta€ susceptibility a inelaling the teal party’ andiniginary pon ys watng = over the sate magnetite Ma given frequency enables reconstraction of (the quasi-static mogncteation fo which indicates a diferent nonlineanty between liquid sample (47.2 mg Fe,O nanopaniles in 80 yl. wate) and the sold ane Instead of the directly measurable ma, we characterized ac susee jntozinaty part 7" as a representative parameter to estimate the finite gradient AmAH at a given Ff, As shown in Fie. Mb). depends on the frequency, in addition to the applied Hic. This frequency dependence underestimates the AmisHt slope for the frequencies above 100 Hz, Particularly, the effective relaxa ion frequeney at which Tupimam, ws obviously shifted 104 higher frequency when increasing Hl from 0 to $0 Oe for instance, indicating 2 feitependtent relaxation dynamics 13]. The corresponding finite-superparamagnetism of the sample ts shown by [iE MGs which depicts the m'(a) curve reconstructed from the de fied-strength deperulence of yo. Them” ‘lined late as a quasi-static magnetization which slightly changes after a de field induction, thus the actual re tion response ma (Hx) seems to be estimable by the low-fiequency mi.) Fig. He) also shows t n'a) carve of liquid saruple at 20 His the most nonlinear curve. The fantcr observed by comparing mit) curves of liquid fighlighting the tsmportant tole of I However, the thermal infhience tnward Fegard to de suscepubilty evaluated. from selaxation dynamics by statistically compar ven frequency FIGURE, Plibility Zu consisting of real part y' and ar difference of the nonlinearity can be and solid samples, for the same particle number, thus ‘ian particle-kineties toward the nonlinearity. of Hment-relaration within each single py mma) curve, we theretore di Hany the de field-tocked mag magnetization cle cannot be neglected. With ished the static fiekd-lependei zation Vectors to those are oscillating at a> (ates may atop ot ent fob \ ened: f RESULTS AND DISCUSSION Dispersing magnetic nanoparticles which have been sterically stabilized with a surface modification (¢.. polymeric coating) into a liquid medium (¢g,, water) enables thermal energy to activate random Brownian motions of the particles within the medium. Once the static magnetic-field is applied, the suspended particles experience Zeeman energy which creates magnetopotentiat energy depending on the direction oftheir magnetization to the | €e anghed fe Ts ize Penta ery Weick sm nun hee meezan vets thrsh Cs ii either moment rotation oF physical rotation, thus Further introicing two other contributing energies: the directional. > & “Eependent anisotropy enetgy and Mie Finetic energy’ proportional to the rotational friction losses. Correspondingly, the relaxation dynamics of the particles is mainly defined by how lags those four eontributing energies (ie. thermal, ‘magnetopotential, anisotropic and kinetis energies) are compared to each other. AS illustrated in the particle energy aim (Fig. 2). for a uniaxial anisotropic nanoparticle having relatively large size, thermal energy at room temperature may’ be insufticiont 19 fh ct thus the Brownian Kinetics such the ETON ATT TN sae | onesie ston tthe de eh ae 2 same dseon tothe) GRIT Tow TumnetopaoaT emery_On the conta. sucien high Held siength gives more energy fo he Farle GraNeTSTMNE ME AMTSNTOFES Theres ber hal STAT Monch dynamics, However, the particles may “Teach Tair MagETATgTAATS GquMibrmum the Fieldandced potential ensray is extremely large. In this case, either the particles or their moments are magnet ly immobilized INée! relaxation STN, Anisotropy enerey = KyVm sin? 8 } Thermal energy. kT -——— rownian relaxation, Ne Oem M1 oa or no vt Roxane ‘Magnetopotential energy weil cos 8 oO 1 ~ jm 1 2 tno}, Vy = dD} Vin FIGURE 2 Energy diagram of ferromagneticenanoparicl wit single-dorsin structure and a uniaxial anisotropy identifies {four encrsies defining the relaxation behavior ofthe particle (4, Néol relaxation with time constant ty er Brownian relaxation ‘sth tim under a given static magneticfield. Thormal energy i defined s linea multiplication of the ambient tonperature tothe Boltzmann constant As. Magretporentil enenge is defined as negative eross-prouct of magnetic moeneat sm=maAov and the applied field H Ha *AH.votrapy energy ts peoporional to the anisetopic constant Ke ad the primary particle volume V. Te felt-snduced linetic energy ¥8 urate tothe triton loss of a rotating hydrodynamic volume Vs with rotation angle # and angular (measurement) frequency cy, under miedium Viscosity 4a our experiments, applying a low oscillatory field tg he statically: magnetized panicles is supposed to tigger fl the foaonal relaxaon of the particles under ermal influence, pancularly the physical rotation, Hence, the going Brownian parvele-hinetes cat be characterized by changing the applied frequency 1 RIUNTME Tortora RE-20 Hz described in Fig ey Thorncal F eateunal mcg Bel > Directional depend anisetrepy energy Con - 2. ran 4 ee Acta Ven) o be — tation rickiars vee Eg _ ated to Sole P ekiele ok ata ) pr eset As 2h koe, 2a MM bigh [reqs - Faia as Brownian . experrencer pauctian fv yp pluysign becomes exponentially decreasing for de field strength Hae > 10 Oclavhereas it is relatively constant for Mi-<10 Oe, ‘The decreasing Zac indicates that the oscillation of magnetization due to thermally activated partilé-kineties as well as moment-dynamics becomes small. Meanwhile, for de susceptibility zac which is defined as the ratio of quasi- Static magnetization m” to Ha trend was found to be similar to zac with a less decrement at f7i.>10 Oe. With regard to the particle polydispersity, the decrease of zz. above 10 Ov may represent an increase of the number of the compleicly magnetized particles. Hypothetically, the resulting difference between ya and Zac is associable with the ratio of particles that are magnetically stabilized in the direction of the applied de field. Based on Fig. 3(b) showing the susceptibility difference Ay=zi-fac for 0.02, 2, and 20 kHz of the sampling frequencies, 4y obviously increases at H.>10 Oe, then it peaks ata certain Hue. This maximum Ay indicates that the relaxation dynamics of the particles statistically becomes steady under the static field, This finding introduces an effective field-strength which is minimally required to align all magnetization vectors of the suspended particles to the de field-direction. For our ferrofluid sample having 15.7 nm in average particle-size, the effective field-strength ‘was about 86 Oe at 20 He, further raised to 130 Oe for 20 kHz, showing a frequency dependence. This characteristic ‘esponse is addressable to the evolutional relaxation mode from Brownian to Néel relaxation (14). To this point, we further plotted the effective field-strength against the frequency range, and interestingly found two flat parts in the curve shown in Fig. 3(¢). According to the hypothetical energy diagram shown in Fig. 2, these two frequency- independent features are supposed to be the minimum field-strength to switch and steadily keep the magnetization veetor of each particle in the Hic direction, involving physical and moment rotations. 003 oor 0 Ts . * zp wale 8 8 A 2 i EL ntsrime i 4 4 x r'. The effective relaxation time f. equal to (cars) tara)" where ty and ry are Brownian and Néeltime-constants, respectively. However, itis bractically difficult to precisely specify both relaxations. Unfortunately, our sample seems to show only a sinle “effective reloation-frequency f = (2ne)" according to Fig. Ib). From the frequency dependence of effective meth in Fig, 3c). nevertheless, we were able to further distinguish the possible frequency range of both "eliatons by characterizing the existing energy bares, TiamalGy. barrier existing in a superparamagnetic ferrofluid is a borderline of two fundamental relaxatio: nerey-bartier Kus tesponsibe for limiting the fcld-strength dependent partelera the well-known anisotropic rotatability under an oscillatory 2021-4field at low frequency [14]. With regard to the particle-size distribution, we mechanism between Brownian and Nécl relaxations under an increasing field-strength, is a statistical process rather than the physical one. This hypothesis means that the transitional relaxation with changing relaxation time constant is considered as a size-dominant behavior of the particles. Shown in Fig. 1(b), for instance, such fi dependent Brownian relaxation [17] does not mean that the particle rotation is being accelerated in a high fi strength. The faster effective relaxation-time, in this ease, implies that the smaller particles act dominantly, associable with the change in relaxation symmetry of 7" (y') curve [12]. Based on Fig. 3(c), we therefore emphasize the role of thermal energy ka" for ferromagnetic nanoparticles as the kinetic energy-barrier separating the initial Brownian relaxation from the effective relaxation, at low frequency range particularly, The coexisting anisotropic energy-barrier additionally sorts Néel relaxation from the effective relaxation. Referring to Fig. 2, thermal energy is estimable by kyT = meHi/n and anisotropy energy is by KuV = mille. Here, me is the resultant moment of m clustered-particles having the average particle-moment mip, whereas Hi and [1, are the effective field-strength corresponding to kinetic and anisotropic barriers, respectively. Due to the large activation energy-ratio, the position of His lower than H, as shown in Fig. 3(c). Owing to these findings, the differential magnetometry seems capable of selectively distinguishing Brownian kinetics from moment dynamics in a ferrofluid. nsider that the actual switching CONCLUSION ‘The Brownian particle-kinetics in a superparamagnetic ferrofluid changes under the static magnetic-field, indicated by the shift of effective relaxation-frequency. To further understand this statistical phenomenon, we proposed a differential magnetometry to analyze the difference between de and ac susceptibilities in correlation with the statistical comparison between the steady and the oscillating magnetization vectors, for a given frequency range and static field-strength. The susceptibility difference was Inter found to be maximum at the effective field-strength from which the coexisting kinetic energy-barrier was identified. The kinetic energy-barrier which contributes to isolating the transitional relaxation between Brownian and Néel relaxations, is none but the thermal energy affecting both particle and moment dynamics. In summary, our findings emphasizes that there is a maximum allowable field- strength to effectively manipulate Brownian particle-kinetics in a superparamagnetic ferrofluid, without significant interferences of Néel relaxation. Toward liquid-phase biomedical applications, this practical concem is of correlation with field-strength optimization, Particularly for a magneto-immunoassay utilizing the spectral-shift of Brownian relaxation, understanding the kinetic energy-barrier may give a reference on how strong the field-strength should be optimized to improve magnetic signals of the analyte-immobilized magnetic nanoparticles. ACKNOWLEDGMENTS: This work was supported by Research Promotion Department, Tokyo Institute of Technology, under research grant No, 28KEN-164, REFERENCES 1. Q.A. Pankhurst, J. Connolly, S. K. Jones, and J. Dobson, J. Phys. D: Appl. Phys. 36, R167-RISI (2003). 2. T. Neuberger, B. Schopf, H. Hofmann, M. Hofmann, and B. von Rechenberg, J. Magn. Magn, Mater. 293, 483-496 (2005). au J. Wei, K. E, Aifantis, Y. Fan, Q. Feng, F.-Z. Cui, F, Watari, Biomed, Mater. Res. 104, 1552-4965 4. ELA. Périgo, G. He n F EA pice G: Hemey, O. Sandre, D, Ortega, E. Garaio, F. Plazaola, and F. J. Teran, Appl. Phys. Rev. 2, 5. JH. Lee, J. Jang, J. Choi, S, H. Moon, Nanotechnol. 6, 418-422 (201 1), 6. R. Weissleder, M, Nahrendorf, and M. J. Pitt 7. B.Zheng, T. Vazin, P. W. Goodwill, A. Cor Rep. §, 14055 (2015) J. Llandro, J. Pabfreyman, A. fonescu, C. Hl. W. Bame: S. Noh, J. Kim, J.-G. Kim, 1S. Kim, K. 1, Park, and J. Cheon, Nat tet, Nat. Mater. 13, 125-138 (2014), nway, A. Verma, E. U. Saritas, D. Schaffer, and S. M. Conolly, Sei 's, Med, Biol. Eng. Comput, 48, 977-998 (2010). 2021-5