Self-assembly of multiferroic core-shell composites using DNA functionalized nanoparticles.

Ferrite-ferroelectric core-shell nanoparticles were prepared by deoxyribonucleic acid (DNA) assisted self-assembly and the strained mediated magneto-electric (ME) interactions between the ferroic phases were studied. The nanoparticle type and size were varied and the DNA linker sequence was also varied. Two kinds of particles, one with 600 nm barium titanate (BTO) core and 200 nm nickel ferrite (NFO) shell and another with 200 nm BTO core and 50 nm nickel cobalt ferrite (NCFO) shell were prepared. The particles were linked by three different oligomeric DNA containing 19, 18 or 30 base pairs. The core-shell structure was evident from electron microscopy and scanning microwave microscopy images. Films and disks of the core-shell particles were assembled in a magnetic field and used for measurements of low frequency ME voltage coefficient (MEVC) and magnet-dielectric effect. The MEVC data on films indicate that particles assembled with DNA with 30 base pairs exhibit the strongest ME coupling suggesting a more fully integrated heterogenous nanocomposite and the weakest interaction for DNA with 18 base pairs. These results indicate that the longer linker region in DNA is the key factor for forming better composites. This result may be due to the irregular shape of the nanoparticles. Longer DNA strands would be able to bridge better generating more linkages. Shorter strands would not able to bridge the irregularly shaped particles as well and therefore result in linkages and less heterogeneity in the composites.

Sensitivity Enhancement in Magnetic Sensors Based on Ferroelectric-Bimorphs and Multiferroic Composites.

Multiferroic composites with ferromagnetic and ferroelectric phases have been studied in recent years for use as sensors of AC and DC magnetic fields. Their operation is based on magneto-electric (ME) coupling between the electric and magnetic subsystems and is mediated by mechanical strain. Such sensors for AC magnetic fields require a bias magnetic field to achieve pT-sensitivity. Novel magnetic sensors with a permanent magnet proof mass, either on a ferroelectric bimorph or a ferromagnetic-ferroelectric composite, are discussed. In both types, the interaction between the applied AC magnetic field and remnant magnetization of the magnet results in a mechanical strain and a voltage response in the ferroelectric. Our studies have been performed on sensors with a Nd-Fe-B permanent magnet proof mass on (i) a bimorph of oppositely-poled lead zirconate titanate (PZT) platelets and (ii) a layered multiferroic composite of PZT-Metglas-Ni. The sensors have been characterized in terms of sensitivity and equivalent magnetic noise N. Noise N in both type of sensors is on the order of 200 pT/√Hz at 1 Hz, a factor of 10 improvement compared to multiferroic sensors without a proof mass. When the AC magnetic field is applied at the bending resonance for the bimorph, the measured N ≈ 700 pT/√Hz. We discuss models based on magneto-electro-mechanical coupling at low frequency and bending resonance in the sensors and theoretical estimates of ME voltage coefficients are in very good agreement with the data.

Multiferroic Core-Shell Nanofibers, Assembly in a Magnetic Field, and Studies on Magneto-Electric Interactions.

Ferromagnetic-ferroelectric nanocomposites are of interest for realizing strong strain-mediated coupling between electric and magnetic subsystems due to a high surface area-to-volume ratio. This report is on the synthesis of nickel ferrite (NFO)-barium titanate (BTO) core-shell nanofibers, magnetic field assisted assembly into superstructures, and studies on magneto-electric (ME) interactions. Electrospinning techniques were used to prepare coaxial fibers of 0.5-1.5 micron in diameter. The core-shell structure of annealed fibers was confirmed by electron microscopy and scanning probe microscopy. The fibers were assembled into discs and films in a uniform magnetic field or in a field gradient. Studies on ME coupling in the assembled films and discs were done by magnetic field (H)-induced polarization, magneto-dielectric effects at low frequencies and at 16-24 GHz, and low-frequency ME voltage coefficients (MEVC). We measured ~2-7% change in remnant polarization and in the permittivity for H = 7 kOe, and a MEVC of 0.4 mV/cm Oe at 30 Hz. A model has been developed for low-frequency ME effects in an assembly of fibers and takes into account dipole-dipole interactions between the fibers and fiber discontinuity. Theoretical estimates for the low-frequency MEVC have been compared with the data. These results indicate strong ME coupling in superstructures of the core-shell fibers.

Poly (vinylidene fluoride) / Poly (acrylonitrile)-based Superior Hydrophobic Piezoelectric Solid Derived by Aligned Carbon Nanotube in Electrospinning: Fabrication, the Phase Conversion and Surface Energy.

Multifunctional materials have attracted many interests from both fundamental and practical aspects, such as field-effect transistor, electric protection, transducers and biosensor. Here we demonstrated the first superior hydrophobic piezoelectric surface based on the polymer blend of polyvinylidene fluoride (PVDF)-polyacrilonitrile (PAN) assisted with functionalized multiwalled nanotubes (MWNTs), by a modified electrospinning method. Typically the ß-phase polyvinylidene fluoride (PVDF) was considered as the excellent piezoelectric and pyroelectric materials. However, polar ß-phase of PVDF exhibited a natural high hydrophilicity. As a well-known fact, the wettability of the surface is dominated by two major factors: surface composition and surface roughness. The significant conversions derived by the incorporation of MWNTs, from nonpolar α-phase to highly polar ß-phase of PVDF, were confirmed by FTIR. Meanwhile, the effects of MWNTs on the improvement of the roughness and the hydrophobicity of polymer blend were evaluated by atomic force microscopy (AFM) and contact angle (CA). Molar free energy of wetting of the polymer nanocomposite decreases with increasing the wt.% of MWNTs. All molar free energy of wetting of PVDF-PAN/MWNTs were negative, which means the non-wettability of film. The combination of surface roughness and low-surface-energy modification in nanostructured composites leads to high hydrophobicity. Particularly, fabrication of superior hydrophobic surfaces not only has fundamental interest but also various possible functional applications in micro- and nano-materials and devices.