Surface Modification of Magnetoactive Elastomers by Laser Micromachining.

It has been recently demonstrated that laser micromachining of magnetoactive elastomers is a very convenient method for fabricating dynamic surface microstructures with magnetically tunable properties, such as wettability and surface reflectivity. In this study, we investigate the impact of the micromachining process on the fabricated material's structural properties and its chemical composition. By employing scanning electron microscopy, we investigate changes in size distribution and spatial arrangement of carbonyl iron microparticles dispersed in the polydimethylsiloxane (PDMS) matrix as a function of laser irradiation. Based on the images obtained by a low vacuum secondary electron detector, we analyze modifications of the surface topography. The results show that most profound modifications occur during the low-exposure (8 J/cm2) treatment of the surface with the laser beam. Our findings provide important insights for developing theoretical models of functional properties of laser-sculptured microstructures from magnetoactive elastomers.

Transient Response of Macroscopic Deformation of Magnetoactive Elastomeric Cylinders in Uniform Magnetic Fields.

Significant deformations of bodies made from compliant magnetoactive elastomers (MAE) in magnetic fields make these materials promising for applications in magnetically controlled actuators for soft robotics. Reported experimental research in this context was devoted to the behaviour in the quasi-static magnetic field, but the transient dynamics are of great practical importance. This paper presents an experimental study of the transient response of apparent longitudinal and transverse strains of a family of isotropic and anisotropic MAE cylinders with six different aspect ratios in time-varying uniform magnetic fields. The time dependence of the magnetic field has a trapezoidal form, where the rate of both legs is varied between 52 and 757 kA/(s·m) and the maximum magnetic field takes three values between 153 and 505 kA/m. It is proposed to introduce four characteristic times: two for the delay of the transient response during increasing and decreasing magnetic field, as well as two for rise and fall times. To facilitate the comparison between different magnetic field rates, these characteristic times are further normalized on the rise time of the magnetic field ramp. The dependence of the normalized characteristic times on the aspect ratio, the magnetic field slew rate, maximum magnetic field values, initial internal structure (isotropic versus anisotropic specimens) and weight fraction of the soft-magnetic filler are obtained and discussed in detail. The normalized magnetostrictive hysteresis loop is introduced, and used to explain why the normalized delay times vary with changing experimental parameters.

Dynamically tunable lamellar surface structures from magnetoactive elastomers driven by a uniform magnetic field.

Stimuli responsive materials are key ingredients for any application that requires dynamically tunable or on-demand responses. In this work we report experimental and theoretical investigation of magnetic-field driven modifications of soft-magnetic elastomers whose surface was processed by laser ablation into lamellar microstructures that can be manipulated by a uniform magnetic field. We present a minimal hybrid model that elucidates the associated deflection process of the lamellae and explains the lamellar structure frustration in terms of dipolar magnetic forces arising from the neighbouring lamellae. We experimentally determine the magnitude of the deflection as a function of magnetic flux density and explore the dynamic response of lamellae to fast changes in a magnetic field. A relationship between the deflection of lamellae and modifications of the optical reflectance of the lamellar structures is resolved.

Theoretical Modeling of Magnetoactive Elastomers on Different Scales: A State-of-the-Art Review.

A review of the latest theoretical advances in the description of magnetomechanical effects and phenomena observed in magnetoactive elastomers (MAEs), i.e., polymer networks filled with magnetic micro- and/or nanoparticles, under the action of external magnetic fields is presented. Theoretical modeling of magnetomechanical coupling is considered on various spatial scales: from the behavior of individual magnetic particles constrained in an elastic medium to the mechanical properties of an MAE sample as a whole. It is demonstrated how theoretical models enable qualitative and quantitative interpretation of experimental results. The limitations and challenges of current approaches are discussed and some information about the most promising lines of research in this area is provided. The review is aimed at specialists involved in the study of not only the magnetomechanical properties of MAEs, but also a wide range of other physical phenomena occurring in magnetic polymer composites in external magnetic fields.

Microstructured Magnetoactive Elastomers for Switchable Wettability.

We demonstrate the control of wettability of non-structured and microstructured magnetoactive elastomers (MAEs) by magnetic field. The synthesized composite materials have a concentration of carbonyl iron particles of 75 wt.% (≈27 vol.%) and three different stiffnesses of the elastomer matrix. A new method of fabrication of MAE coatings on plastic substrates is presented, which allows one to enhance the response of the apparent contact angle to the magnetic field by exposing the particle-enriched side of MAEs to water. A magnetic field is not applied during crosslinking. The highest variation of the contact angle from (113 ± 1)° in zero field up to (156 ± 2)° at about 400 mT is achieved in the MAE sample with the softest matrix. Several lamellar and pillared MAE structures are fabricated by laser micromachining. The lateral dimension of surface structures is about 50 µm and the depth varies between 3 µm and 60 µm. A systematic investigation of the effects of parameters of laser processing (laser power and the number of passages of the laser beam) on the wetting behavior of these structures in the absence and presence of a magnetic field is performed. In particular, strong anisotropy of the wetting behavior of lamellar structures is observed. The results are qualitatively discussed in the framework of the Wenzel and Cassie-Baxter models. Finally, directions of further research on magnetically controlled wettability of microstructured MAE surfaces are outlined. The obtained results may be useful for the development of magnetically controlled smart surfaces for droplet-based microfluidics.

Multiferroic Cantilevers Containing a Magnetoactive Elastomer: Magnetoelectric Response to Low-Frequency Magnetic Fields of Triangular and Sinusoidal Waveform.

In this work, multiferroic cantilevers comprise a layer of a magnetoactive elastomer (MAE) and a commercially available piezoelectric polymer-based vibration sensor. The structures are fixed at one end in the horizontal plane and the magnetic field is applied vertically. First, the magnetoelectric (ME) response to uniform, triangle-wave magnetic fields with five different slew rates is investigated experimentally. Time and field dependences of the generated voltage, electric charge, and observed mechanical deflection are obtained and compared for four different thicknesses of the MAE layer. The ME responses to triangular and sinusoidal wave excitations are examined in contrast. Second, the ME response at low frequencies (≤3 Hz) is studied by the standard method of harmonic magnetic field modulation. The highest ME coupling coefficient is observed in the bias magnetic field strength of ≈73 kA/m and it is estimated to be about 3.3 ns/m (ME voltage coefficient ≈ 25 V/A) at theoretically vanishing modulation frequency (f→0 Hz). Presented results demonstrate that the investigated heterostructures are promising for applications as magnetic-field sensors and energy harvesting devices.

CCN2/CTGF-A Modulator of the Optic Nerve Head Astrocyte.

In primary open-angle glaucoma (POAG), a neurodegenerative disease of the optic nerve (ON) and leading cause of blindness, the optic nerve head (ONH) undergoes marked structural extracellular matrix (ECM) changes, which contribute to its permanent deformation and to degeneration of ON axons. The remodeling process of the ECM causes changes in the biomechanical properties of the ONH and the peripapillary sclera, which is accompanied by an increased reactivity of the resident astrocytes. The molecular factors involved in the remodeling process belong to the Transforming growth factor (TGF)-ß superfamily, especially TGF-ß2. In previous publications we showed that TGF-ß2 induced ECM alterations are mediated by Cellular Communication Network Factor (CCN)2/Connective Tissue Growth Factor (CTGF) and recently we showed that CCN2/CTGF is expressed by astrocytes of the ON under normal conditions. In this study we wanted to get a better understanding of the function of CCN2/CTGF under normal and pathologic conditions. To this end, we analyzed the glial lamina and peripapillary sclera of CCN2/CTGF overexpressing mice and studied the effect of CCN2/CTGF and increasing substratum stiffness on murine ON astrocytes in vitro. We observed enhanced astrocyte reactivity in the ONH, increased ECM protein synthesis in the peripapillary sclera and increased Ccn2/Ctgf expression in the ONH during the pathologic development in situ. CCN2/CTGF treatment of primary murine ON astrocytes induced a higher migration rate, and increase of ECM proteins including fibronectin, elastin and collagen type III. Furthermore, the astrocytes responded to stiffer substratum with increased glial fibrillary acidic protein, vimentin, actin and CCN2/CTGF synthesis. Finally, we observed the reinforced appearance of CCN2/CTGF in the lamina cribrosa of glaucomatous patients. We conclude that reactive changes in ONH astrocytes, induced by the altered biomechanical characteristics of the region, give rise to a self-amplifying process that includes increased TGF-ß2/CCN2/CTGF signaling and leads to the synthesis of ECM molecules and cytoskeleton proteins, a process that in turn augments the stiffness at the ONH. Such a scenario may finally result in a vicious circle in the pathogenesis of POAG. The transgenic CTGF-overexpressing mouse model might be an optimal model to study the chronic pathological POAG changes in the ONH.

Reconfigurable Surface Micropatterns Based on the Magnetic Field-Induced Shape Memory Effect in Magnetoactive Elastomers.

A surface relief grating with a period of 30 µm is embossed onto the surface of magnetoactive elastomer (MAE) samples in the presence of a moderate magnetic field of about 180 mT. The grating, which is represented as a set of parallel stripes with two different amplitude reflectivity coefficients, is detected via diffraction of a laser beam in the reflection configuration. Due to the magnetic-field-induced plasticity effect, the grating persists on the MAE surface for at least 90 h if the magnetic field remains present. When the magnetic field is removed, the diffraction efficiency vanishes in a few minutes. The described effect is much more pronounced in MAE samples with larger content of iron filler (80 wt%) than in the samples with lower content of iron filler (70 wt%). A simple theoretical model is proposed to describe the observed dependence of the diffraction efficiency on the applied magnetic field. Possible applications of MAEs as magnetically reconfigurable diffractive optical elements are discussed. It is proposed that the described experimental method can be used as a convenient tool for investigations of the dynamics of magnetically induced plasticity of MAEs on the micrometer scale.

Magnetoelectric Response of Laminated Cantilevers Comprising a Magnetoactive Elastomer and a Piezoelectric Polymer, in Pulsed Uniform Magnetic Fields.

The voltage response to pulsed uniform magnetic fields and the accompanying bending deformations of laminated cantilever structures are investigated experimentally in detail. The structures comprise a magnetoactive elastomer (MAE) slab and a commercially available piezoelectric polymer multilayer. The magnetic field is applied vertically and the laminated structures are customarily fixed in the horizontal plane or, alternatively, slightly tilted upwards or downwards. Six different MAE compositions incorporating three concentrations of carbonyl iron particles (70 wt%, 75 wt% and 80 wt%) and two elastomer matrices of different stiffness are used. The dependences of the generated voltage and the cantilever's deflection on the composition of the MAE layer and its thickness are obtained. The appearance of the voltage between the electrodes of a piezoelectric material upon application of a magnetic field is considered as a manifestation of the direct magnetoelectric (ME) effect in a composite laminated structure. The ME voltage response increases with the increasing total quantity of the soft-magnetic filler in the MAE layer. The relationship between the generated voltage and the cantilever's deflection is established. The highest observed peak voltage around 5.5 V is about 8.5-fold higher than previously reported values. The quasi-static ME voltage coefficient for this type of ME heterostructures is about 50 V/A in the magnetic field of ≈100 kA/m, obtained for the first time. The results could be useful for the development of magnetic field sensors and energy harvesting devices relying on these novel polymer composites.

Ceramic-Heterostructure-Based Magnetoelectric Voltage Transformer with an Adjustable Transformation Ratio.

A voltage transformer employing the magnetoelectric effect in a composite ceramic heterostructure with layers of a magnetostrictive nickel-cobalt ferrite and a piezoelectric lead zirconate-titanate is described. In contrast to electromagnetic and piezoelectric transformers, a unique feature of the presented transformer is the possibility of tuning the voltage transformation ratio K using a dc magnetic field. The dependences of the transformer characteristics on the frequency and the amplitude of the input voltage, the strength of the control magnetic field and the load resistance are investigated. The transformer operates in the voltage range between 0 and 112 V, and the voltage transformation ratio K is tuned between 0 and 14.1 when the control field H changes between 0 and 6.4 kA/m. The power at the transformer output reached 63 mW, and the power conversion efficiency was 34%. The methods for calculation of the frequency response, and the field and load characteristics of the transformer are proposed. The ways to improve performance characteristics of magnetoelectric transformers and their possible application areas are discussed.

Giant Extensional Strain of Magnetoactive Elastomeric Cylinders in Uniform Magnetic Fields.

Elongations of magnetoactive elastomers (MAEs) under ascending-descending uniform magnetic fields were studied experimentally using a laboratory apparatus specifically designed to measure large extensional strains (up to 20%) in compliant MAEs. In the literature, such a phenomenon is usually denoted as giant magnetostriction. The synthesized cylindrical MAE samples were based on polydimethylsiloxane matrices filled with micrometer-sized particles of carbonyl iron. The impact of both the macroscopic shape factor of the samples and their magneto-mechanical characteristics were evaluated. For this purpose, the aspect ratio of the MAE cylindrical samples, the concentration of magnetic particles in MAEs and the effective shear modulus were systematically varied. It was shown that the magnetically induced elongation of MAE cylinders in the maximum magnetic field of about 400 kA/m, applied along the cylinder axis, grew with the increasing aspect ratio. The effect of the sample composition is discussed in terms of magnetic filler rearrangements in magnetic fields and the observed experimental tendencies are rationalized by simple theoretical estimates. The obtained results can be used for the design of new smart materials with magnetic-field-controlled deformation properties, e.g., for soft robotics.

Effective Medium Theory for the Elastic Properties of Composite Materials with Various Percolation Thresholds.

It is discussed that the classical effective medium theory for the elastic properties of random heterogeneous materials is not congruous with the effective medium theory for the electrical conductivity. In particular, when describing the elastic and electro-conductive properties of a strongly inhomogeneous two-phase composite material, the steep rise of effective parameters occurs at different concentrations. To achieve the logical concordance between the cross-property relations, a modification of the effective medium theory of the elastic properties is introduced. It is shown that the qualitative conclusions of the theory do not change, while a possibility of describing a broader class of composite materials with various percolation thresholds arises. It is determined under what conditions there is an elasticity theory analogue of the Dykhne formula for the effective conductivity. The theoretical results are supported by known experiments and show improvement over the existing approach. The introduction of the theory with the variable percolation threshold paves the way for describing the magnetorheological properties of magnetoactive elastomers. A similar approach has been recently used for the description of magneto-dielectric and magnetic properties.

Anisotropic Magnetoelectric Effect in a Planar Heterostructure Comprising Piezoelectric Ceramics and Magnetostrictive Fibrous Composite.

The direct magnetoelectric (ME) effect is investigated in a planar structure comprising mechanically coupled layers of a magnetostrictive fibrous composite (MFC) and a piezoelectric ceramics (lead zirconate titanate, PZT). The MFC is an array of Ni-wires with a diameter of 200 µm that are aligned parallel to each other in a single layer. The wires are separated by a distance of 250 or 500 µm and fixed in a polyamide matrix. The structure was placed in a tangential constant field H and was excited by an alternating magnetic field h parallel to H, while the voltage generated by the PZT layer was measured. The resulting field dependences of the magnetization M(H) and the magnetostriction λ(H) were determined by the orientation of the field H in the plane of the structure and the distance between the Ni-wires. The ME coupling coefficient of the structure decreased from 4.8 to 0.25 V/A when the orientation of H was changed from parallel to perpendicular to Ni-wires. With an increase in the excitation field amplitude h, a nonlinear ME effect in the output voltage, namely frequency doubling, was observed. The frequency and field dependences of the efficiency of the ME transduction in the MFC-piezoelectric heterostructure are well described by the existing theory.

Magnetodielectric Response of Soft Magnetoactive Elastomers: Effects of Filler Concentration and Measurement Frequency.

The magnetodielectric response of magnetoactive elastomers (MAEs) in its dependence on filler concentration, magnetic field, and test frequency is studied experimentally. MAEs are synthesized on the basis of a silicone matrix filled with spherical carbonyl iron particles characterized by a mean diameter of 4.5 µm. The concentration of the magnetic filler within composite materials is equal to 70, 75, and 80 mass%. The effective lossless permittivity ε' as well as the dielectric loss tanδ grow significantly when the magnetic field increases. The permittivity increases and the dielectric loss decreases with increasing filler concentration. In the measurement frequency range between 1 kHz and 200 kHz, the frequency hardly affects the values of ε' and tanδ in the absence of a magnetic field. However, both parameters decrease considerably with the growing frequency in a constant magnetic field. The more strongly the magnetic field is applied, the larger the change in permittivity and loss tangent at the same test frequency is observed. An equivalent circuit formulation qualitatively describes the main tendencies of the magnetodielectric response.

Effect of Material Composition on Tunable Surface Roughness of Magnetoactive Elastomers.

We investigated magnetic-field-induced modifications of the surface roughness of magnetoactive elastomers (MAEs) with four material compositions incorporating two concentrations of ferromagnetic microparticles (70 wt% and 80 wt%) and exhibiting two shear storage moduli of the resulting composite material (about 10 kPa and 30 kPa). The analysis was primarily based on spread optical reflection measurements. The surfaces of all four materials were found to be very smooth in the absence of magnetic field (RMS roughness below 50 nm). A maximal field-induced roughness modification (approximately 1 µm/T) was observed for the softer material with the lower filler concentration, and a minimal modification (less than 50 nm/T) was observed for the harder material with the higher filler concentration. All four materials showed a significant decrease in the total optical reflectivity with an increasing magnetic field as well. This effect is attributed to the existence of a distinct surface layer that is depleted of microparticles in the absence of a magnetic field but becomes filled with particles in the presence of the field. We analyzed the temporal response of the reflective properties to the switching on and off of the magnetic field and found switching-on response times of around 0.1 s and switching-off response times in the range of 0.3⁻0.6 s. These observations provide new insight into the magnetic-field-induced surface restructuring of MAEs and may be useful for the development of magnetically reconfigurable elastomeric optical surfaces.

Renormalization of the critical exponent for the shear modulus of magnetoactive elastomers.

It is shown that the critical exponent for the effective shear modulus of a composite medium where a compliant polymer matrix is filled with ferromagnetic particles may significantly depend on the external magnetic field. The physical consequence of this dependence is the critical behavior of the relative magnetorheological effect.

Temperature Dependence of the Resonant Magnetoelectric Effect in Layered Heterostructures.

The dependence of the resonant direct magnetoelectric effect on temperature is studied experimentally in planar composite structures. Samples of rectangular shapes with dimensions of 5 mm × 20 mm employed ferromagnetic layers of either an amorphous (metallic glass) alloy or nickel with a thickness of 20-200 µm and piezoelectric layers of single crystalline langatate material or lead zirconate titanate piezoelectric ceramics with a thickness of 500 µm. The temperature of the samples was varied in a range between 120 and 390 K by blowing a gaseous nitrogen stream around them. It is shown that the effective characteristics of the magnetoelectric effect-such as the mechanical resonance frequency fr, the quality factor Q and the magnitude of the magnetoelectric coefficient αE at the resonance frequency-are contingent on temperature. The interrelations between the temperature changes of the characteristics of the magnetoelectric effect and the temperature variations of the following material parameters-Young's modulus Y, the acoustic quality factor of individual layers, the dielectric constant ε, the piezoelectric modulus d of the piezoelectric layer as well as the piezomagnetic coefficients λ(n) of the ferromagnetic layer-are established. The effect of temperature on the characteristics of the nonlinear magnetoelectric effect is observed for the first time. The results can be useful for designing magnetoelectric heterostructures with specified temperature characteristics, in particular, for the development of thermally stabilized magnetoelectric devices.

Magnetorheological response of highly filled magnetoactive elastomers from perspective of mechanical energy density: Fractal aggregates above the nanometer scale?

The dynamic shear modulus of magnetoactive elastomers containing 70 and 80 mass % of carbonyl iron microparticles is measured as a function of strain amplitude via dynamic torsion oscillations in various magnetic fields. The results are presented in terms of the mechanical energy density and considered in the framework of the conventional Kraus model. The form exponent of the Kraus model is further related to a physical model of Huber et al. [Huber et al., J. Phys.: Condens. Matter 8, 409 (1996)10.1088/0953-8984/8/29/003] that uses a realistic representation for the cluster network possessing fractal structure. Two mechanical loading regimes are identified. At small strain amplitudes the exponent ß of the Kraus model changes in an externally applied magnetic field due to rearrangement of ferromagnetic-filler particles, while at large strain amplitudes, the exponent ß seems to be independent of the magnetic field. The critical mechanical energy characterizing the transition between these two regimes grows with the increasing magnetic field. Similarities between agglomeration and deagglomeration of magnetic filler under simultaneously applied magnetic field and mechanical shear and the concept of jamming transition are discussed. It is proposed that the magnetic field should be considered as an additional parameter to the jamming phase diagram of rubbers filled with magnetic particles.

Effect of single-particle magnetostriction on the shear modulus of compliant magnetoactive elastomers.

The influence of an external magnetic field on the static shear strain and the effective shear modulus of a magnetoactive elastomer (MAE) is studied theoretically in the framework of a recently introduced approach to the single-particle magnetostriction mechanism [V. M. Kalita et al., Phys. Rev. E 93, 062503 (2016)10.1103/PhysRevE.93.062503]. The planar problem of magnetostriction in an MAE with magnetically soft inclusions in the form of a thin disk (platelet) having the magnetic anisotropy in the plane of this disk is solved analytically. An external magnetic field acts with torques on magnetic filler particles, creates mechanical stresses in the vicinity of inclusions, induces shear strain, and increases the effective shear modulus of these composite materials. It is shown that the largest effect of the magnetic field on the effective shear modulus should be expected in MAEs with soft elastomer matrices, where the shear modulus of the matrix is less than the magnetic anisotropy constant of inclusions. It is derived that the effective shear modulus is nonlinearly dependent on the external magnetic field and approaches the saturation value in magnetic fields exceeding the field of particle anisotropy. It is shown that model calculations of the effective shear modulus correspond to a phenomenological definition of effective elastic moduli and magnetoelastic coupling constants. The obtained theoretical results compare well with known experimental data. Determination of effective elastic coefficients in MAEs and their dependence on magnetic field is discussed. The concentration dependence of the effective shear modulus at higher filler concentrations has been estimated using the method of Padé approximants, which predicts that both the absolute and relative changes of the magnetic-field-dependent effective shear modulus will significantly increase with the growing concentration of filler particles.

Single-particle mechanism of magnetostriction in magnetoactive elastomers.

Magnetoactive elastomers (MAEs) are composite materials comprised of micrometer-sized ferromagnetic particles in a nonmagnetic elastomer matrix. A single-particle mechanism of magnetostriction in MAEs, assuming the rotation of a soft magnetic, mechanically rigid particle with uniaxial magnetic anisotropy in magnetic fields is identified and considered theoretically within the framework of an alternative model. In this mechanism, the total magnetic anisotropy energy of the filling particles in the matrix is the sum over single particles. Matrix displacements in the vicinity of the particle and the resulting direction of the magnetization vector are calculated. The effect of matrix deformation is pronounced well if the magnetic anisotropy coefficient K is much larger than the shear modulus µ of the elastic matrix. The feasibility of the proposed magnetostriction mechanism in soft magnetoactive elastomers and gels is elucidated. The magnetic-field-induced internal stresses in the matrix lead to effects of magnetodeformation and may increase the elastic moduli of these composite materials.