Mika Latikka

Switchable Static and Dynamic Self-Assembly of Magnetic Droplets on Superhydrophobic Surfaces

Magnetic Self-Assembly During self-assembly, objects spontaneously assemble into larger ordered patterns as observed, for example, in the phase segregation of block copolymers or the assembly of micrometer-sized objects and components in electronics. In dynamic self-assembly, the ordered patterns require an external energy source, but still form because of intrinsic interactions within the system. Timonen et al. (p. 253; see the Perspective by Hermans et al.) studied the organization of magnetic droplets, in the form of a ferrofluid, placed on a low-friction surface. A time-varying magnetic field transformed the statically arranged droplets into a dynamic pattern. Magnetic droplets oscillate between static and dynamic self-assembly patterns in a magnetic field. [Also see Perspective by Hermans et al.] Self-assembly is a process in which interacting bodies are autonomously driven into ordered structures. Static structures such as crystals often form through simple energy minimization, whereas dynamic ones require continuous energy input to grow and sustain. Dynamic systems are ubiquitous in nature and biology but have proven challenging to understand and engineer. Here, we bridge the gap from static to dynamic self-assembly by introducing a model system based on ferrofluid droplets on superhydrophobic surfaces. The droplets self-assemble under a static external magnetic field into simple patterns that can be switched to complicated dynamic dissipative structures by applying a time-varying magnetic field. The transition between the static and dynamic patterns involves kinetic trapping and shows complexity that can be directly visualized.

Free-decay and resonant methods for investigating the fundamental limit of superhydrophobicity

The recently demonstrated extremely water-repellent surfaces with contact angles close to 180° with nearly zero hysteresis approach the fundamental limit of non-wetting. The measurement of the small but non-zero energy dissipation of a droplet moving on such a surface is not feasible with the contemporary methods, although it would be needed for optimized technological applications related to dirt repellency, microfluidics and functional surfaces. Here we show that magnetically controlled freely decaying and resonant oscillations of water droplets doped with superparamagnetic nanoparticles allow quantification of the energy dissipation as a function of normal force. Two dissipative forces are identified at a precision of ~ 10 nN, one related to contact angle hysteresis near the three-phase contact line and the other to viscous dissipation near the droplet-solid interface. The method is adaptable to common optical goniometers and facilitates systematic and quantitative investigations of dynamical superhydrophobicity, defects and inhomogeneities on extremely superhydrophobic surfaces.

Friction and Wetting Transitions of Magnetic Droplets on Micropillared Superhydrophobic Surfaces

Reliable characterization of wetting properties is essential for the development and optimization of superhydrophobic surfaces. Here, the dynamics of superhydrophobicity is studied including droplet friction and wetting transitions by using droplet oscillations on micropillared surfaces. Analyzing droplet oscillations by high-speed camera makes it possible to obtain energy dissipation parameters such as contact angle hysteresis force and viscous damping coefficients, which indicate pinning and viscous losses, respectively. It is shown that the dissipative forces increase with increasing solid fraction and magnetic force. For 10 µm diameter pillars, the solid fraction range within which droplet oscillations are possible is between 0.97% and 2.18%. Beyond the upper limit, the oscillations become heavily damped due to high friction force. Below the lower limit, the droplet is no longer supported by the pillar tops and undergoes a Cassie-Wenzel transition. This transition is found to occur at lower pressure for a moving droplet than for a static droplet. The findings can help to optimize micropillared surfaces for low-friction droplet transport.

Structural diversity in metal–organic nanoparticles based on iron isopropoxide treated lignin

The magnetic nature of iron-containing nanoparticles enables multiple high-end applications. Metal alkoxides are a highly reactive chemical species, which are widely used in ceramics and sol–gel manufacture. However, their use with organic molecules has been mostly limited to catalytic purposes due to their highly reactive nature. Lignin is the second most abundant biopolymer in the world-rich in OH groups and amenable to highly stable colloid nanoparticle formation by a simple solvent exchange process. Here we show that the reaction between iron isopropoxide and lignin in tetrahydrofuran (THF) solution produces metal–organic nanoparticles with tunable morphologies, ranging from hollow and solid nanospheres to open network structures. The immediate condensation reaction between lignin and iron isopropoxide as well as the resulting structure morphology can be controlled by varying the reaction parameters. Despite iron isopropoxide being highly water sensitive, the formed structures are stable as water suspensions. Our results demonstrate that solution processable metal–organic nanoparticles can be easily produced with macromolecular polyols in an inert solvent, such as THF. This presents a facile method of obtaining various metal–organic nanomaterials, with a wide range of metal alkoxides and organic polyols to choose from. We anticipate that metal–bioorganic sol–gel reactions will produce biocompatible materials with enhanced functionality, such as magnetic, antibacterial and catalytic properties depending on the chosen metal and polyol.

Complexes of Magnetic Nanoparticles with Cellulose Nanocrystals as Regenerable, Highly Efficient, and Selective Platform for Protein Separation

We present an efficient approach to develop cellulose nanocrystal (CNC) hybrids with magnetically responsive Fe3O4 nanoparticles that were synthesized using the (Fe3+/Fe2+) coprecipitation. After 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-catalyzed oxidation of CNC, carbodiimide (EDC/NHS) was used for coupling amine-containing iron oxide nanoparticles that were achieved by dopamine ligand exchange (NH2-Fe3O4 NPs). The as-prepared hybrids (Fe3O4@CNC) were further complexed with Cu(II) ions to produce specific protein binding sites. The performance of magnetically responsive Cu-Fe3O4@CNC hybrids was assessed by selectively separating lysozyme from aqueous media. The hybrid system displayed a remarkable binding capacity with lysozyme of 860.6 ± 14.6 mg/g while near full protein recovery (∼98%) was achieved by simple elution. Moreover, the regeneration of Fe3O4@CNC hybrids and efficient reutilization for protein separation was demonstrated. Finally, lysozyme separation from matrices containing egg white was achieved, thus revealing the specificity and potential of the presented method.

Wetting of ferrofluids: Phenomena and control

Abstract Ferrofluids are liquids exhibiting remarkably strong response to magnetic fields, which leads to fascinating properties useful in various applications. Understanding the wetting properties and spreading of ferrofluids is important for their use in microfluidics and magnetic actuation. However, this is challenging as magnetically induced deformation of the ferrofluid surface can affect contact angles, which are commonly used to characterize wetting properties in other systems. In addition, interaction of the magnetic nanoparticles and solid surface at nanoscale can have surprising effects on ferrofluid spreading. In this review we discuss these issues with focus on interpretation of ferrofluid contact angles. We review recent literature examining ferrofluid wetting phenomena and outline novel wetting related ferrofluid applications. To better understand wetting of ferrofluids, more careful experimental work is needed.

Oscillating Ferrofluid Droplet Microrheology of Liquid-Immersed Sessile Droplets

The damped oscillations of liquid-immersed ferrofluid sessile droplets were studied with high-speed imaging experiments and analytical modeling to develop a novel microrheology technique. Droplet oscillations were induced with an external magnetic field, thereby avoiding transients in the resulting vibrational response of the droplet. By following the droplet relaxation with a high-speed camera, the frequency and relaxation time of the damped harmonic oscillations were measured. We extend upon existing analytical theories to describe our liquid-immersed sessile droplet system, and directly quantify the droplet relaxation with the viscosity of the internal and external fluid as well as the interfacial tension between these. The easily controllable magnetic droplets make our oscillating ferrofluid droplet technique a potential candidate for high-throughput microrheology and tensiometry in the future.