Novel highly elastic magnetic materials for dampers and seals: part II. Material behavior in a magnetic field

The combination of polymers with magnetic particles displays novel and often enhanced properties compared to the traditional materials. They can open up possibilities for new technological applications. The magnetic field sensitive elastomers represent a new type of composites consisting of small particles, usually from nanometer range to micron range, dispersed in a highly elastic polymeric matrix. In this paper, we show that in the presence of built‐in magnetic particles it is possible to tune the elastic modulus by an external magnetic field. We propose a phenomenological equation to describe the effect of the external magnetic field on the elastic modulus. We demonstrate the engineering potential of new materials on the examples of two devices. The first one is a new type of seals fundamentally different from those used before. In the simplest case, the sealing assembly includes a magnetoelastic strip and a permanent magnet. They attract due to the magnetic forces. This ensures that due to high elasticity of the proposed composites and good adhesion properties, the strip of magnetoelastic will adopt the shape of the surface to be sealed, this fact leading to an excellent sealing. Another straightforward application of the magnetic composites is based on their magnetic field dependent elastic modulus. Namely, we demonstrate in this paper the possible application of these materials as adjustable vibration dampers. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of a homogeneous magnetic field on the mechanical behavior of soft magnetic elastomers under compression

The mechanical properties of new magnetic composite materials were studied. The above materials represent rubbery silicon matrices filled with magnetic microparticles of metallic iron or magnetite. In homogeneous magnetic fields with an intensity of up to 0.4 T, the shear modulus of the composites was abnormally high (up to 10 000%). The variation of elastic properties of new materials on the type and volume content of the magnetic filler was investigated. In the presence of a sufficiently strong magnetic field, the above composites were shown to behave as elastoplastic materials with strengthening.     

Smart nanocomposite polymer gels

The combination of polymers with nanomaterials displays novel and often enhanced properties compared to the traditional materials. They can open up possibilities for new technological applications. The magnetic polymer gel represents a new type of composites consisting of small magnetic particles, usually from the nanometer range to the micron range, dispersed in a highly elastic polymeric gel matrix. Combination of magnetic and elastic properties leads to a number of striking phenomena that are exhibited in response to impressed magnetic fields. Giant deformational effects, high elasticity, anisotropic properties, temporary reinforcement and quick response to magnetic field open new opportunities for using such materials for various applications.     

Modification of new polymer materials based on aminostyrene by irradiation

The ultra-violet (UV) irradiation induced modification of the mechanical and optical properties of several polymer composites containing 4-aminostyrene and glycidyl methacrylate and their dependences on radiation dose, structure and ageing have been investigated. The nano- and microindentation techniques were used for determination of the mechanical parameters of as-grown and irradiated materials. The light-induced structural changes result in an increase of the hardness and elastic modulus of the polymer layers up to five and three times, respectively. It is also shown that the influence of polymer structure is significant. The conditions for improvement, degradation and stabilization of physical properties by UV irradiation were established. Load and depth sensing indentation has proved to be a powerful tool for an accurate estimation of mechanical properties of cross-linking polymer compositions. Variable-energy positron annihilation spectroscopy (slow-positron beam technique) was developed to measure defect depth profiles in the near-surface region. The increase of S-parameter with the increase of nano-hardness and elastic modulus has been determined for these materials.     

Water-annealing regulated protein-based magnetic nanofiber materials: tuning silk structure and properties to enhance cell response under magnetic fields

In this study, flexible silk fibroin protein and biocompatible barium hexaferrite (BaM) nanoparticles were combined and electrospun into nanofibers, and their physical properties could be tuned through the mixing ratios and a water annealing process. Structural analysis indicates that the protein structure of the materials is fully controllable by the annealing process. The mechanical properties of the electrospun composites can be significantly improved by annealing, while the magnetic properties of barium hexaferrite are maintained in the composite. Notably, in the absence of a magnetic field, cell growth increased slightly with increasing BaM content. Application of an external magnetic field during in vitro cell biocompatibility study of the materials demonstrated significantly larger cell growth. We propose a mechanism to explain the effects of water annealing and magnetic field on cell growth. This study indicates that these composite electrospun fibers may be widely used in the biomedical field for controllable cell response through applying different external magnetic fields.     

Preparation and characterization of 3D collagen materials with magnetic properties

In this study 3D collagen materials with magnetic properties were prepared by lyophilization technique. Magnetic particles were synthesized by precipitation of iron (II) sulfate heptahydrate and iron (III) chloride hexahydrate in an aqueous solution of chitosan and then added to a collagen solution. Starch dialdehyde (DAS) was used as a cross-linking agent for the materials. The properties of the obtained materials were studied using infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Additionally, mechanical properties, porosity, density, swelling and moisture content were measured.It was found that 3D composites made from collagen with magnetic particles are hydrophilic with a high swelling ability. Cross-linking of such collagen materials with dialdehyde starch (DAS) alters the swelling degree, porosity and density of materials. The addition of magnetic particles to collagen materials decreases its porosity, and increases the density of the studied materials. Collagen 3D materials with magnetic particles are rigid and inflexible. Magnetic properties of the 3D collagen materials containing magnetic particles were confirmed by the interaction of this material with a magnet.     

Properties of ultrahighly filled composites based on polymers and ground rubber

The stress-strain and strength properties of ultrahighly filled composites based on thermoplastic polymers and ground rubber wastes are studied. The content of the elastic filler is higher than 70 wt%. As is shown, introduction of minor amounts of the plastic polymer, which serves as the binder for the filler particles, makes it possible to improve the strength properties of ultrahighly filled composites and to prepare materials of a desired thickness. A correlation between the stress-strain properties of the plastic polymer-rubber systems and the effective viscosity of the matrix polymer is established. When a polymer with homogeneous deformation and good adhesion to the elastic filler is used as the matrix, the resultant composites are characterized by properties close to those of vulcanized rubbers. A new method is proposed for processing of ground rubber wastes and preparation of materials that are similar to hard rubbers.     

Fabrication,characterization and X-band microwave absorption properties of PAni/Fe3O4/PVA nanofiber composites materials

This work presents a study of microwave absorption properties of PAni/Fe₃O₄/PVA nanofiber composites with different ratio of Fe₃O₄ nanoparticles. The morphology of the composites nanofibers study by Field Emission Scanning Electron Microscopes (FESEM) and Transmission Electron Microscope (TEM) showed that the low content of Fe₃O₄ nanoparticles presence in the composites nanofibers indicates very much uniform surface, in the composites nanofiber without many bends, but some bends develop at higher content of Fe₃O₄ nanoparticles as indicated in the TEM image. Image-J software was used to further investigate the diameter of the composites nanofiber and found to be in the range of 152 to 195 nm. The nanofiber composites show excellent electric and magnetic properties and therefore vary with the addition of Fe₃O₄ nanoparticles in the composites nanofiber. In addition the PAni/Fe₃O₄/PVA composites nanofibers were further characterized by X-ray diffraction spectra (XRD) and Four Transformation infrared spectra (FTIR). The XRD pattern shows the presence of PAni nanotubes containing Fe₃O₄ nanoparticles by indicating peaks at 23.4⁰ and 35.43⁰ which was further supported by FTIR analysis. Microwave vector network analyzers (MVNA) were used to estimate the microwave absorption properties of the composites nanofibers. The absorption parameters was found to be −6.4 dB at 12.9 GHz within the range of X-band microwave absorption frequency, this reflection loss is attributed to the multiple absorption mechanisms as a result of the improved of impedance matching between dielectric and magnetic loss of the absorbent materials demonstrating that these materials can be used as protective material for electromagnetic radiation.     

Anisotropy of elastic properties and thermal conductivity of Al2O3/h-BN composites

The presence of h-BN phase in the composites, in which it is fulfilling a role of a solid lubricant, causes the appearance of the anisotropy of the elastic properties and thermal properties. In order to assess the extent of the phenomenon, velocity changes of ultrasonic wave propagation were measured and thermal conductivity changes were researched. Measurements were carried out on composites of alumina matrix, which had h-BN introduced in an amount of 0–30 vol.%. The study included measurements of the speed of propagation of ultrasound waves and thermal conductivity, which were made in two directions, namely, perpendicular and parallel directions to the axis of compression. Strong dependence of the thermal conductivity anisotropy of the phase composition of materials was revealed.     

Interactions modes and physical properties in transition metal chalcogenolene-based molecular materials

Molecule-based materials are extremely versatile materials as they can be built from specifically designed building blocks with the desired size, shape, charge and electronic properties which determine their intermolecular interactions and, thus, their organization in the solid. The intermolecular interactions, therefore, in particular van der Waals interactions, π–π and π–d interactions, H-bonding, etc., play a crucial role in self-assembling these pre-designed molecular units and may provide a powerful way to afford layered mono- and multifunctional molecular materials with new or unknown physical properties. In this review the relationship between interaction modes and physical properties of organic/inorganic hybrids based on transition metal complexes with chalcogenolene ligands will be examined and an outlook will be proposed. With this goal, magnetic materials, highly conducting and metallic single-component materials containing dithiolene complex building blocks, multifunctional materials where the dithiolene complex is the magnetic or conducting component in addition to more complex systems involving other types of building block such as the metal oxalate complexes, will be discussed.     

Conducting polymers: Efficient thermoelectric materials

This review highlights the recent progress made in the area of thermoelectric (TE) applications of conducting polymers and related composites. Several examples of such materials and their TE properties are discussed. TE properties of new poly(2,7‐carbazole) derivatives are highlighted. References are also made to carbon nanotube/polymer composites and their improved electrical and TE performance. Studies on polymer/inorganic materials composites have also taken a step forward and have shown very promising TE properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Cellulose/iron oxide hybrids as multifunctional pigments in thermoplastic starch based materials

Cellulose/iron oxide hybrids were prepared by the controlled hydrolysis of FeC₂O₄ in the presence of vegetable and bacterial cellulose fibres as substrates. By varying the relative amount of FeC₂O₄ and NaOH, either hematite or magnetic iron oxides were grown at the cellulose fibres surfaces. This chemical strategy was used for the production of a number of materials, whose coloristic properties associated to their reinforcement role allowed their use as new hybrid pigments for thermoplastic starch (TPS) based products. The TPS reinforced materials were characterized by several techniques in order to evaluate: the morphology and the compatibility between the matrix and the fillers; the mechanical reinforcement effect of the cellulose/iron oxide pigments on TPS and the coloristic properties of the composites. All materials showed good dispersion and strong adhesion for the cellulose/iron oxide nanocomposites in the TPS matrix thus resulting in improved mechanical properties.     

Playing with organic radicals as building blocks for functional molecular materials

The literature has shown numerous contributions on the synthesis and physicochemical properties of persistent organic radicals but there are a lesser number of reports about their use as building blocks for obtaining molecular magnetic materials exhibiting an additional and useful physical property or function. These materials show promise for applications in spintronics as well as bistable memory devices and sensing materials. This critical review provides an up-to-date survey to this new generation of multifunctional magnetic materials. For this, a detailed revision of the most common families of persistent organic radicals-nitroxide, triphenylmethyl, verdazyl, phenalenyl, and dithiadiazolyl-so far reported will be presented, classified into three different sections: materials with magnetic, conducting and optical properties. An additional section reporting switchable materials based on these radicals is presented (257 references).     

Magnetic clusters and conducting molecular materials from polyoxometalates

The relevance of polyoxometalate chemistry in molecular magnetism and molecular materials is discussed.In the first part we show that these molecular metal-oxides provide remarkable examples of magnetic clusters for which the nuclearity and the topology can be varied in a controlled manner. They provide ideal models for the study of magnetic interactions in clusters, and for the study of the interplay between electron delocalization and magnetic interactions. In the second part we illustrate the use of polyoxoanions as inorganic components of new hybrid molecular materials having conducting and/or magnetic properties. Two kinds of materials are presented namely, crystalline hybrid salts in which the electron donors are organic molecules of the TTF type or organometallic complexes as the decamethylferrocene, and films formed by polyoxometalates embedded in conducting polymers (of the polypyrrole type).     

Organozeolite materials and their properties

Attempts in developing organozeolites, namely microporous and mesoporous crystalline inorganic-organic composites with a zeolite-like three-dimensional framework and organic moieties covalently connected to the framework, are briefly reviewed. MCM-41 type mesoporous materials modified by organic functional groups have been prepared by use of organosiloxane as a part of Si sources and by post-modification of the purely inorganic materials using organosiloxane. Also, the incorporation of organic moieties into the zeolite frameworks has been tried. Recently, several novel metal organophosphonates with a three-dimensional framework, which can be regarded as organozeolites, have been prepared. Along with these new attempts, the authors' studies in preparation, structural analysis and gas adsorption properties of microporous aluminomethylphosphonates are introduced.     

X-ray diffraction and morphology of crystalline,hard, elastic materials

Summary X-ray diffraction and electron microscopic results on several crystalline polymers which demonstrate elastic properties (polypropylene, Celcon^®, poly-4-methyl-pentene) are reported. Photographic small angle X-ray diffraction techniques provided considerable qualitative information, concerning the morphological features of these elastic materials both as extruded, annealed and during extension. Lamellar thickness, thickness distribution and perfection of lamellae could be estimated. Lateral order features and orientation of the lamellar structures were obtainable from the sharpness and length of the equatorial wide angle diffraction arcs. Electron microscopic results essentially confirm the morphological features postulated on the basis of the X-ray results. These morphological features are discussed in terms of a general structural model which appears consistent with the mechanical properties of these materials.

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Zusammenfassung Röntgenbeugung und elektronenmikroskopische Daten von einigen kristallinen Polymerprodukten mit elastischen Eigenschaften (Polypropylen, Celcon, Poly-4-methylpenten) werden berichtet. Die photographische Röntgen-Kleinwinkelmethode liefert wichtige qualitative Messungen der morphologischen Struktur dieser elastischen Materialien in den Zuständen sowohl wie hergestellt als auch nach Tempern und während des Dehnungsprozesses. Die Dicke der Lamellen, ihre Dikkenverteilung und die Güte der Lamellen konnten abgeschätzt werden. Die laterale Ordnung und die Orientierung der Lamellen kann aus Weitwinkelbeugungsdaten abgeleitet werden. Die Elektronenmikroskopie bestätigt die Morphologie, die aus Röntgendaten folgt. Ein allgemeines Strukturmodel dieser Morphologie, das im Einklang mit den mechanischen Eigenschaften dieser Produkte steht, wird diskutiert.

     

Polymer/silicate composites: new materials for subsurface permeable reactive barriers

Investigations were performed into the suitability of novel composites to serve as materials for subsurface permeable reactive barriers (PRBs). These new materials are Type I composites—they are preformed organic polymers embedded in an inorganic matrix without significant covalent bonding between the components. The required properties for these materials to function efficiently are: (1) a tunable water passing rate to approximate the hydraulic conductivity of the subsurface environment where the PRB will be placed, (2) sufficient mechanical strength (both wet and dry) to maintain barrier integrity, (3) the ability to incorporate selective metal sequestration agents so that they remain active—yet do not leach from the barrier, and (4) to be deployable through direct injection methods such that trenching is not needed. Additionally, there is a need to keep the technology as low cost as possible, while remaining reliable. Results recently obtained in our laboratory show that our materials, remarkably, exhibit all of these properties and show great promise as vadose zone deployable PRBs.     

Manipulation of the magnetic properties of magnetite-silica nanocomposite materials by controlled Stober synthesis

The paper describes the synthesis and characterization of the magnetic properties of magnetite/silica nanocomposites using a modified Stober method. Magnetite nanoparticles averaging 8-10 nm in diameter and stabilized with oleic acid in toluene were used as the magnetic component of the nanocomposites. SQUID magnetic measurements and ferromagnetic resonance spectroscopy measurements were performed at each stage of the synthesis to understand the properties of the formed composites. Changes of blocking temperature in ZFC/FC SQUID curves correlated with corresponding changes of the resonance field in the ferromagnetic spectra of the sample at each stage of formation. The paper concludes that it is possible to manipulate the magnetic properties of silica/magnetite composite materials by controlling their surface properties and silica coating thickness.     

Synthesis and application of inorganic/organic composite materials

A new type of inorganic-organic composite has been developed using organic monomeric or polymerizable silanes (with appropriate organic groupings like double bonds or epoxides) as monomers or in situ prepared or separately added nano-scale ceramic or metal particles. Due to the small size of the particulate phase, these composites are still highly transparent but show properties at least partially to be attributed to the inorganic phase. The introduction of special functions into these materials has been used for the fabrication of interesting functions like non-linear optical properties, low surface free energy coatings, controlled release properties or special mechanical properties (scratch resistance).     

Dielectric,magnetic and mechanical properties of ferrite composites

The dielectric and magnetic properties of carbonyl—iron (CI) and nickel zinc ferrite polymer composites were studied with respect to the ferrite particulate content and microwave frequency. From the experimental data and using empirical models that relate the composite dielectric and magnetic properties, the respective dielectric and magnetic properties of the neat fillers were estimated. The tensile properties of the particulate composites comprising CI were shown to follow qualitatively Mooney's equation for the elastic modulus. The tensile strength of an elastomeric polyurethane and PVC composites containing CI increased with particulate content, while the elongation to break decreased with filler content. SEM micrographs of tensile fracture surfaces indicated that somewhat better adhesion is obtained in the case of the polyurethane-based composites compared to the PVC ones.