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Ferrofluid

A ferrofluid is a colloidal suspension of nanoscale ferromagnetic or ferrimagnetic particles, typically iron oxide such as magnetite (Fe₃O₄), dispersed in a non-magnetic carrier liquid like water, oil, or kerosene, stabilized by surfactants to prevent agglomeration and maintain fluidity. These particles, usually 3–15 nm in diameter, render the fluid superparamagnetic, meaning it exhibits no residual magnetization without an external field but becomes strongly magnetized and responsive when one is applied, often forming characteristic spiky patterns aligned with magnetic field lines. Invented in 1963 by engineer Stephen Papell, ferrofluids were initially developed to address the challenge of managing liquid propellants in zero-gravity conditions, where alone could not reliably draw fuel to pumps; instead, would direct the fluid. Although not used in as originally intended, the technology spurred commercial advancements, including the founding of Ferrofluidics Corporation in the , which pioneered applications in rotary shaft seals for semiconductors and vacuum systems by the mid-1970s. The field of ferrohydrodynamics, formalizing the behavior of these fluids under magnetic influences, was established shortly after by researchers like Ronald E. Rosensweig, leading to foundational theories on their rheological and thermal properties. Key properties of ferrofluids include magnetoviscosity, where increases under due to particle and , and enhanced thermal conductivity, which can rise by up to 300% in strong fields depending on particle concentration and composition. They are synthesized primarily via co-precipitation of iron salts in alkaline conditions or for precise size control, ensuring stability against sedimentation through of the nanoparticles. These attributes enable diverse applications, from uses like in speakers and in to biomedical roles such as (MRI) —where particles like 8 nm Fe₃O₄ improve —and targeted or for , heating tumors to 41–46°C via alternating . Emerging uses also include , such as removing from water, and from .

Fundamentals

Definition and Composition

A ferrofluid is a colloidal liquid that becomes strongly magnetized in the presence of a , consisting of nanoscale ferromagnetic or ferrimagnetic particles suspended in a carrier fluid. These particles, typically in the size range of 3 to 15 nanometers, exhibit superparamagnetic behavior, allowing the fluid to respond rapidly to external without retaining once the field is removed. This unique combination of fluidity and magnetic responsiveness distinguishes ferrofluids from other magnetic materials. The core component of a ferrofluid is the , most commonly iron oxides such as (Fe₃O₄) or (γ-Fe₂O₃), which provide the ferromagnetic properties. These nanoparticles are single-domain structures, ensuring high magnetic saturation while minimizing . Other compositions include ferrites doped with metals like , , , or to tailor magnetic strength and . The is critical, as diameters around 10 nm optimize colloidal and prevent aggregation due to overpowering magnetic interactions. The carrier fluid forms the continuous , suspending the nanoparticles and determining the ferrofluid's and characteristics; common options include nonpolar hydrocarbons like or for oil-based ferrofluids, and polar solvents like or for aqueous variants. To maintain and prevent from van der Waals forces or magnetic attractions, or stabilizers coat the nanoparticles, creating a steric or electrostatic barrier. is widely used in nonaqueous ferrofluids due to its amphiphilic nature, with its hydrophobic tail extending into the carrier and polar head binding to the particle surface; in aqueous systems, ionic like or provide electrostatic repulsion. The overall volume fraction of nanoparticles typically ranges from 5% to 20% to balance magnetic response with . Originally developed in the by researchers for applications in space, ferrofluids have since evolved with advanced techniques to incorporate specialized carriers, such as perfluorocarbons for fluorous variants, enabling or targeted functionalities.

Historical Development

The invention of ferrofluids traces back to the early , when engineer Stephen S. Papell developed a stable magnetic to solve the problem of controlling liquid rocket propellants in microgravity. Papell's approach involved suspending finely divided particles in a low-viscosity carrier, such as , stabilized to prevent and allow magnetic manipulation for directing fuel to turbopumps without mechanical pumps. This innovation, patented in 1965 as a low-viscosity magnetic , represented the first successful of a durable ferrofluid, though it was not adopted for space missions due to the industry's shift toward solid propellants. Concurrently, theoretical foundations for ferrofluid behavior emerged in 1964 with the seminal paper by Joseph L. Neuringer and Ronald E. Rosensweig, which introduced ferrohydrodynamics as a for the and of strongly polarizable magnetic continua. This work formalized the equations governing magnetic body forces and in ferrofluids, enabling predictive modeling of their response to applied fields and laying the groundwork for subsequent research. Papell's experimental advancements and Neuringer-Rosensweig's marked the birth of ferrofluid , transitioning from suspensions explored in the 1930s—such as unstable magnetic inks—to engineered colloidal systems. Commercialization accelerated in 1968 with the establishment of Ferrofluidics Corporation by Ronald E. Rosensweig and Ronald Moskowitz, who leveraged NASA-funded research at AVCO Corporation to produce stable ferrofluids for industrial applications like hermetic seals in rotating shafts. By the early 1970s, ferrofluids gained traction in for vibrations in loudspeakers and providing non-contact seals, with Rosensweig's leadership at AVCO advancing magnetization stability and scalability. A key theoretical milestone came in 1972 when M.I. Shliomis extended ferrohydrodynamics to include magnetoviscous effects, explaining the field-induced increase in effective due to particle alignment in dilute suspensions. Papell's contributions were later honored in 1982 with a $15,000 award from NASA's Inventions and Contributions Board, underscoring the technology's pivot from aerospace to diverse engineering uses.

Preparation

Synthesis of Nanoparticles

The synthesis of nanoparticles forms the foundational step in ferrofluid preparation, where , primarily (Fe₃O₄) or (γ-Fe₂O₃), are produced at the nanoscale (typically 3–15 nm) to ensure superparamagnetic behavior and colloidal stability. These particles must exhibit high and minimal aggregation to enable effective dispersion in carrier fluids. Common synthesis routes include chemical and physical methods, with co-precipitation being the most widely adopted due to its simplicity and scalability. Co-precipitation involves the simultaneous precipitation of iron(II) and iron(III) salts, such as FeCl₂ and FeCl₃, in an aqueous solution under alkaline conditions (e.g., using NaOH or NH₄OH) and inert atmosphere to prevent oxidation. The reaction proceeds as: \text{Fe}^{2+} + 2\text{Fe}^{3+} + 8\text{OH}^- \rightarrow \text{Fe}_3\text{O}_4 + 4\text{H}_2\text{O} This method yields particles of 10–20 nm with high yield but offers limited control over size distribution, often resulting in polydispersity. It is favored for industrial applications due to low cost and ease, though post-synthesis purification is needed to remove unreacted ions. Variations, such as ultrasound-assisted co-precipitation, improve uniformity by enhancing mixing. Thermal decomposition, a high-temperature organic-phase , decomposes iron organometallic precursors like (Fe(CO)₅) or iron(III) acetylacetonate (Fe(acac)₃) in high-boiling solvents (e.g., phenyl ether) under inert conditions, often with for size control. Seminal work by Sun et al. demonstrated precise tuning of from 3 nm to 16 nm by varying reaction parameters, producing highly monodisperse, crystalline nanoparticles with saturation up to 70 emu/g. Advantages include superior size uniformity and crystallinity, essential for advanced ferrofluids, but it requires oxygen-free environments, expensive precursors, and yields smaller batches compared to aqueous methods. Hydrothermal synthesis employs high-pressure, high-temperature aqueous reactions in sealed autoclaves, using iron salts and reducing agents (e.g., ) at 100–200°C to form nanoparticles. This method produces well-crystallized particles of 10–30 with shapes tunable by temperature and , such as cubic or spherical morphologies, and minimizes aggregation through in-situ growth. It offers better phase purity than co-precipitation for single-phase but demands specialized equipment and longer reaction times (hours to days). The sol-gel process involves and of metal alkoxides or inorganic salts (e.g., ) to form a , which gels and is calcined to yield nanoparticles. For , it typically results in 8–50 particles with controllable composition via doping, and it is versatile for hybrid materials, though annealing steps are required to achieve the desired structure. This method excels in producing uniform coatings but can introduce impurities if conditions are not optimized. Microemulsion synthesis utilizes reverse micelles in oil-water systems to confine nanoparticle growth, enabling uniform iron oxide particles of 3–10 nm. This method, often involving precipitation within surfactant-stabilized droplets, provides excellent size control and is suitable for ferrofluids due to in-situ stabilization, though it requires careful phase separation and may involve toxic solvents. Mechanical milling, a top-down physical approach, grinds bulk iron oxides (e.g., hematite) in a ball mill with surfactants or stabilizers to reduce particle size to sub-100 nm (e.g., ~77 nm minimum). It enables large-scale production at low cost and has been used to create ferrofluids with higher saturation magnetization than rapid co-precipitation routes, though it often requires additional sonication to de-agglomerate. This technique is particularly useful for recycling or starting from natural ores but yields broader size distributions.

Stabilization and Surfactants

Stabilization in ferrofluids refers to the processes that maintain the dispersion of , typically iron oxides like (Fe₃O₄), within a liquid, counteracting attractive forces such as van der Waals interactions and magnetic dipole-dipole couplings that lead to and . Without effective stabilization, nanoparticles would cluster, resulting in loss of colloidal properties and diminished responsiveness to . This stability is crucial for practical applications, enabling ferrofluids to remain fluid and uniform over extended periods, sometimes exceeding decades under ambient conditions. Surfactants are amphiphilic molecules that adsorb onto surfaces, forming a protective that introduces repulsive interactions to achieve stabilization. The primary mechanisms are steric repulsion, where surfactant tails extend into the carrier liquid to create an entropic barrier preventing close particle approach, and electrostatic repulsion, generated by charged head groups that induce like-charge interactions between particles. The effectiveness depends on the -to-particle ratio, typically optimized to form a or bilayer, and compatibility with the carrier fluid's polarity; mismatched systems can lead to . Seminal overviews emphasize that proper selection balances these forces, ensuring even in strong up to 10 T. Common surfactants vary by carrier type. In non-aqueous ferrofluids, such as those using or , is widely adopted due to its long chain, which provides robust steric stabilization and affinity for nonpolar solvents; for example, -coated Fe₃O₄ nanoparticles (∼10 nm) yield stable suspensions with zeta potentials around -40 mV. Other options include and fatty acids for similar systems. For aqueous ferrofluids, biocompatible like (a natural polysaccharide) or (PVA) offer steric hindrance in polar media, while ionic agents such as (SDS) or (TMAH) provide electrostatic stabilization through surface charge modification. These choices enable tailored stability for biomedical or engineering uses, with polymer coatings like poly() enhancing longevity in dilute suspensions.

Properties

Magnetic Behavior

Ferrofluids are colloidal suspensions of superparamagnetic nanoparticles, typically magnetite or maghemite with diameters around 10 nm, dispersed in a carrier liquid. These nanoparticles exhibit superparamagnetism, meaning they possess strong magnetic moments but no net magnetization in the absence of an external field due to thermal agitation randomizing their orientations. When an external magnetic field is applied, the particles align with the field, inducing magnetization in the fluid without hysteresis or remanence, allowing reversible control. This behavior enables ferrofluids to respond rapidly to field changes, forming a magnetizable continuum that combines fluid flow with magnetic properties. The magnetization M of a ferrofluid follows the Langevin function, derived from for non-interacting magnetic dipoles. In the low-field limit, the response is linear, characterized by the initial \chi_0, where M \approx \chi_0 H, with H being the strength. As the field increases, saturation magnetization M_s is approached, typically on the order of 10-50 kA/m for common ferrofluids, beyond which further alignment is limited. The full equilibrium magnetization is given by M = M_s \left( \coth \xi - \frac{1}{\xi} \right), where \xi = \frac{\mu_0 m H}{k_B T}, m is the magnetic moment of a nanoparticle, \mu_0 is the vacuum permeability, k_B is Boltzmann's constant, and T is the temperature. This model assumes thermal equilibrium and neglects interparticle interactions, which become significant at high concentrations. Under moderate fields, the aligned nanoparticles form elongated chains or aggregates along field lines, enhancing the effective magnetization and influencing the fluid's overall magnetic profile. The susceptibility depends on particle volume fraction \phi, size distribution, and material, with typical values of \chi_0 ranging from 1 to 10 for engineering ferrofluids. This field-induced structuring is reversible upon field removal, driven by Brownian motion and surfactant stabilization, ensuring the fluid's colloidal integrity. Seminal theoretical frameworks, such as those in ferrohydrodynamics, describe how magnetization couples with fluid velocity and pressure, underpinning applications in seals and actuators.

Rheological and Thermal Characteristics

Ferrofluids exhibit Newtonian behavior in the absence of a , with their primarily governed by the properties of the carrier fluid and the volume fraction of , typically ranging from 2 to 500 mPa·s for dilute suspensions. Upon application of a , the magnetoviscous effect emerges, causing a significant increase in due to the alignment of superparamagnetic nanoparticles into dipolar chains that generate hydrodynamic against the . This enhancement, often by a factor of 2 or more, depends on the field strength, particle concentration, and , as described in early theoretical models by Shliomis, which account for rotational and magnetic torque. Under shear, magnetized ferrofluids display non-Newtonian characteristics, including , where decreases with increasing shear rate as the aligned chains are disrupted and reorient. Unlike magnetorheological fluids with larger particles, ferrofluids lack a true owing to preventing permanent aggregation, though Bingham-like models approximate behavior at low shear rates with an extrapolated that rises linearly with for low concentrations (e.g., φ < 0.1). These properties, detailed in Rosensweig's ferrohydrodynamics framework, enable tunable flow resistance for applications like and dampers. The thermal conductivity of ferrofluids exceeds that of the base fluid, with enhancements proportional to nanoparticle volume fraction (φ), following Maxwell's effective medium theory adapted for magnetic particles: k_{eff} = k_0 \frac{2k_0 + k_p - 2\phi(k_0 - k_p)}{2k_0 + k_p + \phi(k_0 - k_p)}, where k_0 and k_p are the conductivities of the fluid and particles, respectively. For example, additions of 10-20 vol.% Fe₃O₄ nanoparticles can boost conductivity by over 100% in zero field. Magnetic fields further amplify this by inducing anisotropic chain formations that bridge particles, improving heat pathways along the field direction and yielding enhancements up to 300% at high fields (e.g., 0.3 T) and moderate φ (∼6 vol.%). Beyond conduction, ferrofluids support thermomagnetic , where field gradients couple with temperature-induced changes to drive fluid motion, enhancing overall coefficients by 20-50% in enclosed systems like cavities or tubes. This effect, first analyzed by Finlayson, is quantified by the magnetic Ra_m = \frac{\mu_0 \chi H \beta \Delta T L^3}{\eta \kappa}, where χ is , β the of , and other terms standard fluid properties. Such behaviors position ferrofluids as advanced coolants in and electronics.

Instabilities and Patterns

When a ferrofluid is subjected to an external perpendicular to its , the can become unstable above a critical strength, leading to the formation of pronounced surface deformations known as the Rosensweig instability. This phenomenon, first theoretically analyzed by Cowley and Rosensweig, arises from the competition between destabilizing magnetic normal stresses, which concentrate at surface protrusions to amplify perturbations, and stabilizing forces such as and . The critical field for onset depends on fluid properties, including \rho, \sigma, and magnetic susceptibility \chi, and is approximately given by B_c = \sqrt{2 \mu_0 \sqrt{\rho [g](/page/G) \sigma (1 + \chi)}}, where \mu_0 is the and g is ; typical values for water-based ferrofluids yield B_c around 10–20 mT. At supercritical fields, the instability manifests as a regular array of peaks or spikes on the ferrofluid surface, typically arranged in a hexagonal lattice with wavelength \lambda \approx 2\pi \sqrt{\sigma / (\rho g)}, the capillary length, though magnetic effects modify this scale. These spike patterns are self-organized and dynamic, with peaks reaching heights up to several millimeters and exhibiting oscillatory growth before saturating into stable structures; experimental observations confirm hexagonal symmetry as the preferred morphology due to energetic minimization. The patterns are highly sensitive to field strength and frequency (in AC fields), where higher fields promote sharper spikes, and vibrations can induce transitions to square lattices or chaotic states. In configurations with tangential or oblique magnetic fields, different instabilities emerge, often producing striped or labyrinthine patterns rather than peaks. For instance, a parallel to the surface in a thin ferrofluid film destabilizes the interface into rolls or herringbone structures, where the field gradient induces anisotropic stresses that favor elongated deformations aligned with the field direction. In quasi-two-dimensional setups, such as ferrofluid drops confined between plates under a transverse field, labyrinthine patterns form through fingering instabilities at the droplet edge, evolving into interconnected meandering channels due to the interplay of magnetic body forces and interfacial tension; these patterns are observed at field strengths above 50 mT and exhibit universal scaling akin to . Such patterns highlight the versatility of ferrofluids in demonstrating nonlinear hydrodynamic-magnetic coupling, with applications in visualizing field lines and .

Applications

Engineering and Consumer Uses

Ferrofluids are widely employed in for their ability to form dynamic in rotary systems, such as feedthroughs and tandem in equipment, implanters, and epitaxial growth tools, where they create contactless liquid barriers that withstand high speeds and maintain integrity under conditions. These leverage the ferrofluid's to hold it in place via permanent magnets, reducing wear and enabling operation in environments like manufacturing. In bearings and lubricants, ferrofluids provide tunable friction and load-bearing capacity, as seen in computer hard disk drives and cleanroom robots, where they minimize energy loss and extend component life compared to traditional oils. Additionally, ferrofluid-based dampers utilize magnetoviscous effects for vibration control in and systems, offering adjustable forces that improve stability in and precision machinery. In thermal management, ferrofluids enhance efficiency in cooling by increasing thermal conductivity under , allowing for compact designs in high-power devices like LEDs and . For instance, hybrid ferrofluids incorporating Fe₃O₄ nanoparticles with carbon nanotubes achieve higher heat dissipation rates than base fluids, supporting miniaturized systems in and vibrational absorbers. applications use ferrofluids to detect flaws in magnetic materials, such as turbine blades and stainless steels, by revealing surface irregularities under . Consumer applications of ferrofluids prominently feature audio loudspeakers, where the fluid fills the gap between the voice coil and to dissipate —up to 150°C continuously—preventing thermal compression and enabling higher power handling by 20-50% while improving and reducing . This , introduced commercially in the , is standard in tweeters and drivers for systems, , and professional sound equipment. In artistic contexts, ferrofluid enables dynamic sculptures, as pioneered by Sachiko Kodama, who uses computer-controlled electromagnets to manipulate the fluid into organic, evolving shapes mimicking natural forms like tornadoes or sea urchins, as in works such as Morpho Tower (), blending with interactive . Educational consumer products, including visualization kits, allow users to observe patterns and instabilities, fostering learning through hands-on demonstrations.

Biomedical and Research Applications

Ferrofluids, consisting of superparamagnetic nanoparticles (IONPs) dispersed in biocompatible carriers, have emerged as versatile tools in due to their responsiveness to external and tunable surface properties. When coated with materials like (PEG), , or , these fluids exhibit low and high stability in physiological environments, enabling applications in diagnostics, therapy, and targeted interventions. In magnetic resonance imaging (MRI), ferrofluids serve as negative contrast agents, primarily enhancing T2- and T2*-weighted images by shortening relaxation times through effects. Iron oxide-based ferrofluids, such as those with 8-10 nm Fe₃O₄ cores coated with poly(), provide superior contrast compared to agents, allowing detection of small lesions like liver metastases. Seminal work includes the FDA-approved Feridex (ferumoxide), a dextran-coated ferrofluid which was used for liver from the 1990s until its discontinuation in 2009, which accumulates in Kupffer cells to delineate tumors. Recent advancements involve silica or polymer coatings to improve specificity, as demonstrated in studies where water-based ferrofluids achieved improved signal-to-noise ratios in preclinical models. Targeted drug delivery represents a key application, where magnetic fields guide ferrofluids loaded with therapeutics to specific sites, minimizing systemic exposure. For instance, PEG-coated Fe₃O₄ nanoparticles conjugated with enable pH-responsive release in tumor microenvironments (pH ~5.5), with release under alternating magnetic fields while reducing in animal models. Chitosan-stabilized ferrofluids have been used to deliver across the blood-brain barrier, with magnetic targeting increasing accumulation in xenografts. This approach leverages the superparamagnetic behavior to confine delivery, as seen in early seminal studies on magnetically vectored carriers for anticancer agents. Magnetic utilizes the hysteretic heating of ferrofluids under alternating magnetic fields (AMFs) to ablate cancer cells, raising local temperatures to 42-46°C while sparing healthy . Superparamagnetic IONPs, such as oleic acid-coated 12-14 nm particles, induce in tumor cells , as shown in HOS cell studies with Fe-Cr-Nb-B ferrofluids achieving 183 W/g at 45°C. Clinical trials, building on foundational research from the 1990s, have integrated with , where intratumoral injections of dextran-coated ferrofluids enhanced tumor regression by 40% in models under 100 kHz AMFs. Cobalt-doped variants further boost heating efficiency, with values exceeding 500 W/g in optimized formulations. Beyond therapy, ferrofluids facilitate cell separation and biosensing in research settings. In immunomagnetic separation, antibody-functionalized IONPs (e.g., 10 nm Fe₃O₄ with ) capture rare circulating tumor cells with high efficiency under low-gradient fields, aiding diagnostics for and studies. For biosensors, giant magnetoimpedance effects in Fe₃O₄-based ferrofluids enable detection of biomarkers like glucose or pathogens at low levels, with arrays forming under fields for enhanced sensitivity. Antimicrobial applications include Ag-hybrid ferrofluids generating (ROS) to inhibit Escherichia coli and Candida albicans growth at low concentrations. Ongoing research explores magneto-mechanical actuation, where rotating fields (e.g., 80 Oe at 3 Hz) disrupt membranes, reducing viability without , offering a non-thermal alternative to . Multifunctional bio-ferrofluids, incorporating quantum dots or genes, are investigated for combined imaging-delivery platforms, with preclinical data showing improved therapeutic indices in solid tumors. These developments underscore ferrofluids' potential in , though challenges like long-term biodistribution and regulatory validation require further study.

Emerging Technologies

Ferrofluids are increasingly integrated into , enabling the development of adaptive, multifunctional liquid robots capable of precise navigation and manipulation in complex environments. In adaptive ferrofluidic robotic systems, actuation using electromagnetic coils and permanent magnets allows for of , orientation, and deformation, achieving average trajectory errors as low as 0.1621 mm and orientation errors of 1.46° in multiscale luminal structures. These systems leverage the magnetothermal effect for rapid drug release, with capsules achieving 50% release in 45 seconds under high-frequency , demonstrating potential for targeted therapies in simulated blood vessels. Multifunctional liquid further exploit ferrofluids' high and for multi-dimensional via the magneto-Archimedes effect, handling payloads with densities from 1.1 to 8.9 g/cm³, while integrated sensing detects vibrations, flows, and concentrations through changes. Stretchable magnetic materials incorporating ferrofluids as deformable cores in elastomeric channels have advanced soft electromagnetic devices, such as with up to 3.5-fold enhancement and efficiencies reaching 92%. Ferrofluidic properties enable reconfigurable miniature soft machines, where magnetic induces motions like , jumping, and rotating, facilitating applications in confined spaces such as cargo delivery through 3 mm ducts or fluid pumping at 3.9 mm/s using cilia arrays. These developments underscore ferrofluids' role in creating versatile, robots for biomedical interventions, including non-invasive and environmental exploration. In biomedical applications, ferrofluids support advanced magnetic systems, where hybrid (CFD) and models simulate nanocarrier motion in blood under external fields, achieving predictive accuracies with R² values up to 0.99088 using optimized K-nearest neighbor algorithms. This framework, integrating Navier-Stokes and , optimizes nanocarrier design to enhance precision in , minimizing damage to healthy tissues by guiding particles via tunable magnetic gradients. Such modeling reduces reliance on extensive physical experiments, accelerating the translation of ferrofluid-based therapies from lab to clinical use. Ferrofluids also enable emerging technologies, particularly for vibration-based systems in wearable and devices. By sloshing in external magnetic fields, ferrofluids induce voltage through flux changes via , generating mean voltages up to 3.01 mV and powers of 232.56 nW in configurations with high concentrations. These harvesters exhibit broad frequency responses up to 8 Hz without , offering conformable alternatives to rigid generators for low-power applications. For thermal management, magnetic nanofluids like Fe₃O₄-water exhibit magneto-hydrodynamic behaviors in mini-channel heat sinks, enhancing heat transfer by up to 65% in Nusselt number under 2000 G fields through vortex formation and boundary layer disruption. Ribbed channel designs achieve thermal enhancement factors of 2.06 while reducing friction by 86%, optimizing cooling for high-heat-flux electronics like CPUs, with performance plateauing efficiently at 1500–2000 G. This positions ferrofluids as a promising medium for next-generation, field-tunable cooling systems in compact devices.

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