Preparation of Cellulose/Laponite Composite Particles and Their Enhanced Electrorheological Responses.

Cellulose, as a natural polymer with an abundant source, has been widely used in many fields including the electric field responsive medium that we are interested in. In this work, cellulose micron particles were applied as an electrorheological (ER) material. Because of the low ER effect of the raw cellulose, a composite particle of cellulose and Laponite was prepared via a dissolution-regeneration process. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to observe the morphologies and structures of the composite particles, which were different from pristine cellulose and Laponite, respectively. The ER performances of raw cellulose and the prepared composite were measured by an Anton Paar rotational rheometer. It was found that the ER properties of the composite were more superior to those of raw cellulose due to the flake-like shapes of the composite particles with rough surface. Moreover, the sedimentation stability of composite improves drastically, which means better suspension stability.

The Electric Field Responses of Inorganic Ionogels and Poly(ionic liquid)s.

Ionic liquids (ILs) are a class of pure ions with melting points lower than 100 °C. They are getting more and more attention because of their high thermal stability, high ionic conductivity and dielectric properties. The unique dielectric properties aroused by the ion motion of ILs makes ILs-contained inorganics or organics responsive to electric field and have great application potential in smart electrorheological (ER) fluids which can be used as the electro-mechanical interface in engineering devices. In this review, we summarized the recent work of various kinds of ILs-contained inorganic ionogels and poly(ionic liquid)s (PILs) as ER materials including their synthesis methods, ER responses and dielectric analysis. The aim of this work is to highlight the advantage of ILs in the synthesis of dielectric materials and their effects in improving ER responses of the materials in a wide temperature range. It is expected to provide valuable suggestions for the development of ILs-contained inorganics and PILs as electric field responsive materials.

Presence of global and local α-relaxations in an alkyl phosphate glass former.

The dynamics of a molecular glass former, tributyl phosphate (TBP), with an alkyl phosphate structure (three alkyl branches emanating from a polar core of PO4) is studied in the supercooled regime by dielectric and thermal (or enthalpic) relaxations. The dielectric fragility index md and the stretching exponent ßd of the Kohlrausch-Williams-Watts correlation function are determined. Analyses of the enthalpic relaxation data by the Tool-Narayanaswamy-Moynihan-Hodge formalism yield the enthalpic fragility index mH and stretching exponent ßH. The large difference between the dielectric md and the enthalpic mH, as well as between ßd and ßH, is a remarkable finding. The differences are interpreted by the formation of molecular self-assemblies. The interpretation is supported by the quite comparable fragility determined by viscosity and the enthalpic relaxation. The Kirkwood factor calculated at low temperatures is also consistent with the interpretation. The results suggest that the enthalpic relaxation involving the motions of all parts of TBP is global, while the dielectric relaxation detects the local rotation, which might originate from the rotation of the dipole moment of the core. The presence of two structural α-relaxations, one global and one local, with a large difference in dynamics is revealed for the first time in a molecular glass former.

Glass formability in medium-sized molecular systems/pharmaceuticals. I. Thermodynamics vs. kinetics.

Scrutinizing critical thermodynamic and kinetic factors for glass formation and the glass stability of materials would benefit the screening of the glass formers for the industry of glassy materials. The present work aims at elucidating the factors that contribute to the glass formation by investigating medium-sized molecules of pharmaceuticals. Glass transition related thermodynamics and kinetics are performed on the pharmaceuticals using calorimetric, dielectric, and viscosity measurements. The characteristic thermodynamic and kinetic parameters of glass transition are found to reproduce the relations established for small-molecule glass formers. The systematic comparison of the thermodynamic and kinetic contributions to glass formation reveals that the melting-point viscosity is the crucial quantity for the glass formation. Of more interest is the finding of a rough correlation between the melting-point viscosity and the entropy of fusion normalized by the number of beads of the pharmaceuticals, suggesting the thermodynamics can partly manifest its contribution to glass formation via kinetics.

A new secondary relaxation in the rigid and planar 1-methylindole: Evidence from binary mixture studies.

Found in our recent dielectric study of a planar and rigid glass-former, 1-methylindole (1MID), is an unusual secondary relaxation unrelated in its dynamic properties to the structural α-relaxation. We speculated that it originates from the in-plane motion of the molecules, and the supposedly universal Johari-Goldstein (JG) ß-relaxation with strong connection to the structural α-relaxation in rigid glass-formers is not resolved [X. Q. Li et al. J. Chem. Phys. 143, 104505 (2015)]. In this work, dielectric measurements are performed in binary mixtures of 1MID with two aromatics of weak polarity, ethylbenzene (EB) and triphenylethylene (TPE), in the highly viscous regimes near glass transition. EB and TPE have smaller and larger molecular sizes and glass transition temperatures Tg than 1MID, respectively. Strikingly, the results show that the resolved secondary relaxations of 1MID in the two mixtures share the same relaxation time and their temperature dependence as pure 1MID, independent of the mode and degree of dilution. The results indicate that the unusual secondary relaxation is not directly coupled with the α-relaxation, and support the in-plane-rotation interpretation of its origin. On the other hand, the supposedly universal and intermolecular JG ß-relaxation coming from the out-of-plane motion of the planar molecule has weaker dielectric strength, and it cannot be resolved from the more intense in-plane-rotation secondary relaxation because the dipole moment of 1MID lies on the plane.

Core-shell-structured monodisperse copolymer/silica particle suspension and its electrorheological response.

Monodisperse core-shell-structured poly(styrene-co-butyl acrylate-co-[2-(methacryloxy)ethyl] trimethylammonium chloride)/silica (PSBM/SiO2) nanoparticles were applied as new electrorheological (ER) materials in which the particles were dispersed in an insulating oil. These nanoparticles were prepared by the consecutive precipitation of cetyltrimethylammonium bromide and negatively charged tetraethylorthosilicate onto the cationic surfaces of PSBM colloidal particles. The successful deposition of the shell phase of the particles and their morphology was examined by transmission and scanning electron microscopy. Their ER properties were studied with a rotational rheometer under different shear modes: controlled shear rate, steady shear under constant shear rate, and creep test. The silica shell allowed the PSBM/SiO2 particles to exhibit typical ER performance under an applied electric field. The dielectric spectra of the PSBM/SiO2-based ER fluid were also recorded using an LCR meter, which was correlated to the ER performance of the ER fluid.

Comparative study of dynamics in glass forming mixtures of Debye-type N-ethylacetamide with water, alcohol, and amine.

The glass transition and relaxation dynamics in the binary mixtures of a Debye liquid, N-ethylacetamide, with water, monoalcohol, and amine are studied by calorimetric and dielectric measurements in the highly viscous regimes near the glass transition. Calorimetric measurements show the glass transition temperature in the N-ethylacetamide-water mixtures is remarkably enhanced as water is added as high as 70 mol. % before crystallization is detected. A similar increase is also observed in the N-ethylacetamide-rich mixtures with the non-Debye 1,2-propanediamine. However, the dielectric measurements show that the main relaxation in the N-ethylacetamide-water mixtures with water fraction up to 60 mol. % reproduces the dynamic characters of the mixtures constituted by two Debye liquids, N-ethylacetamide and 2-ethyl-1-butanol. The comparison of the calorimetric and dielectric features for the three mixing systems suggests that the Debye relaxation persists in the N-ethylacetamide-water mixtures within the experimentally studied compositions.

Pickering-emulsion-polymerized polystyrene/Fe2O3 composite particles and their magnetoresponsive characteristics.

Core-shell-structured magnetic polystyrene (PS)/inorganic particles were fabricated by Pickering emulsion polymerization using nanosized Fe2O3 particles as a solid stabilizer. Scanning electron microscopy and transmission electron microscopy confirmed the synthesized PS/Fe2O3 particles to be comprised of a PS surface coated with Fe2O3 nanoparticles. The chemical structure of the composite nanospheres was characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The thermal properties of composite nanospheres and corresponding pure polymer were examined by thermogravimetric analysis. The rheological properties of the core-shell-structured magnetic PS/inorganic particles dispersed in silicone oil were investigated under an external magnetic field strength using a rotational rheometer. The particles with extremely lower density than common magnetic particles exhibited solid-like magnetorheological phase characteristics, and the flow curves were fitted to the Cho-Choi-Jhon model of the rheological equation of state.

Chitosan-based double cross-linked ionic hydrogels as a strain and pressure sensor with broad strain-range and high sensitivity.

A conductive hydrogel P(AAm-co-AA)/CS-Fe3+ with double cross-linked networks was fabricated using a one-step polymerization by UV irradiation and a soaking process in Fe(NO3)3 solution. In this hydrogel, the rigid chain of chitosan (CS) and the soft chain of copolymer P(AAm-co-AA) with acrylic acid (AA) and acrylamide (AAm) act as the backbone, among which large amounts of hydrogen bonds are formed by the amino, hydroxyl, and carboxyl groups on the two polymers. Ferric irons (Fe3+) are introduced and form coordination interactions with carboxyl and amino groups of the polymers. The double cross-linked interactions in the system can enhance the tensile strength and toughness of the hydrogel. Thus, the prepared P(AAm-co-AA)/CS-Fe3+ hybrid network hydrogel shows excellent mechanical properties in many aspects: a strength of up to 550 kPa, a broad strain-range up to 800%, fast self-recovery ability (30 min), and low hysteresis strain (<100%). The conductive hydrogel demonstrates high strain sensitivity (gauge factor (GF) = 6.6 at a strain of 700%) as a flexible sensor. Human movements (for example, finger bending, vocal cord vibration, and other human activities) can be sensitively detected using the P(AAm-co-AA)/CS-Fe3+ hydrogel sensor.

Core-shell structured monodisperse poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) coated polystyrene microspheres and their electrorheological response.

We report the successful synthesis of transparent thin film of conducting poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS) coated monodisperse polystyrene (PS) microspheres via a simple physical adsorption route in an aqueous media and their electrorheological (ER) application under an applied electric field. Due to the insulating PS core, the PEDOT/PSS wrapped PS (PEDOT/PSS/PS) particles possess a low volume conductivity appropriately applied as ER active materials. Tested by a rotational rheometer under an applied electric field, the PEDOT/PSS/PS based ER fluid dispersed in a silicone oil shows a typical Bingham-fluid behavior with increased yield stresses according to the increase of electric field strength.

Core-shell structured semiconducting PMMA/polyaniline snowman-like anisotropic microparticles and their electrorheology.

Core-shell structured semiconducting snowman-like particles were synthesized, and their electrorheological (ER) characteristics under an applied electric field were examined. Monodispersed snowman-like poly(methyl methacrylate) (PMMA) particles were fabricated previously using a seed emulsion polymerization procedure. These anisotropic particle-based ER fluids, which were tested using a rotational rheometer, exhibited unusual ER properties in the flow curves at various electric field strengths when analyzed using the Cho-Choi-Jhon model. The dielectric spectra, as supporting data for the ER effect, were measured using a LCR meter. The relaxation time of the ER fluid was relatively shorter than typical ER fluids.

Enhanced Electrorheological Response of Cellulose: A Double Effect of Modification by Urea-Terminated Silane.

As a natural polymer with abundant sources, cellulose was one of the earliest applied electrorheological (ER) materials. However, cellulose-based ER materials have not attracted much attention because of their relatively low ER effect and sensitivity to water. In this study, cellulose rods were decorated with a urea-terminated silane, 1-(3-(trimethoxysilyl) propyl) urea, after being swelled in sodium hydroxide solution. The morphologies and structures of the cellulose particles were investigated using scanning electron microscopy, Fourier-transform infrared spectroscopy and X-ray diffraction, confirming the dramatic differences of the treated cellulose particles from the pristine cellulose. Rheological behaviors of the pristine and modified cellulose particles in silicone oil were observed using a rotational rheometer. It was found that the silane-modified cellulose showed higher ER effect and higher dielectric properties than the pristine cellulose particles, which was not only related to the grafted polar molecules but may also be associated with the porous morphologies of the treated cellulose particles.

Direct Evidence of Relaxation Anisotropy Resolved by High Pressure in a Rigid and Planar Glass Former.

Rigid molecular glass-formers with no internal degrees of freedom nonetheless have a single secondary ß-relaxation. For a rigid and planar molecule, 1-methylindole (1MID), although a secondary relaxation is resolved at ambient pressure, its properties do not conform to the rules established for rigid molecules reported in early studies. By applying pressure to the dielectric spectra of 1MID, we find the single secondary relaxation splits into two. The slower one is pressure sensitive showing connections to the α-relaxation as observed in other rigid molecules, while the faster one is almost pressure insensitive and dominate the loss at ambient pressure. The two secondary relaxations, identified to associate with the out-of-plane and in-plane rotations of the rigid and planar 1MID, are resolved and observed for the first time by increasing density via elevating pressure.

Monodisperse poly(2-methylaniline) coated polystyrene core-shell microspheres fabricated by controlled releasing process and their electrorheological stimuli-response under electric fields.

A core-shell structured electro-responsive electrorheological (ER) particle system comprised of monodisperse poly(2-methylaniline)-coated polystyrene (PS/PMAN) microspheres was fabricated by applying a controlled swelling-releasing technique to pre-fabricated micron-sized PS seeds using a dispersion polymerization method. Compact wrapping of the PS microparticles with semiconducting PMAN without a de-doping process was examined by scanning electron microscopy and transmission electron microscopy. Fourier-transform infrared spectroscopy and thermogravimetric analysis also confirmed the chemical composition and thermal stability of the particles, respectively. Rheological characteristics of the PS/PMAN microsphere based ER fluid dispersed in silicone oil at various electric field strengths revealed a typical ER response under both steady shear flow and dynamic oscillation, demonstrating its mechanism of a conductivity model with a slope of 1.5.

Facile fabrication of Pickering emulsion polymerized polystyrene/laponite composite nanoparticles and their electrorheology.

Polystyrene (PS)/laponite composite nanoparticles were fabricated using a surfactant-free Pickering emulsion polymerization method, in which emulsions of styrene dispersed in water were stabilized by hydrophilic laponite modified with cetyltrimethylammonium bromide. The PS/laponite nanoparticles, of which their surface was covered compactly by laponite clay platelets, were observed by scanning electron microscopy. Fourier-transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis confirmed their chemical composition, crystallographic structure, and thermal properties and weight loss percentage of the laponite located on the surface of the PS particle, respectively. When an external electrical field was applied, the chain-like structure of the laponite coated nano-sized PS particle exhibiting electrorheological characteristics was observed by optical microscopy. The electrorheological performance of the bulk properties was also examined using a rotational rheometer equipped with a high voltage generator.

Generalized yield stress equation for electrorheological fluids.

A new generalized yield stress scaling equation for electrorheological (ER) fluids was developed by introducing the critical electric field (Ec) and material parameter. This equation can be used to describe the dependency of the yield stress on an electric field not only for conventional ER suspensions with a change in slope from 2.0 to 1.5, but also for giant ER fluids with a change in slope from 2.0 to 1.0. The yield stress data obtained from different ER fluid systems with different material parameters was collapsed onto a single curve for the entire range of electric field strengths using the proper scaling method proposed in this study.

Optically transparent electrorheological fluid with urea-modified silica nanoparticles and its haptic display application.

A transparent electrorheological (ER) fluid was fabricated by dispersing urea-modified silica nanoparticles in a mixture of halocarbon oil and silicone oil, whose refractive index could be tuned to be the same as that of the dispersed particles. The ER fluid showed considerable enhancement in shear stress and shear viscosity, as determined by a rotational rheometer, as well as improved dielectric spectra measured using a LCR meter. Morphological and thermal characterization by scanning electron microscopy and thermal gravimetric analysis confirmed the modification by urea. The potential applications of the transparent ER fluid as haptic displays were also investigated.

Carbon nanotube coated snowman-like particles and their electro-responsive characteristics.

We report the fabrication of core-shell structured snowman-like microparticles coated with multi-walled carbon nanotubes and their electro-responsive electrorheological behavior under an applied electric field strength when dispersed in silicone oil. It is observed that they form a chain-like structure, possessing microfluidic potential applications with their solid-like property.

Novel electrorheological properties of a metal-organic framework Cu3(BTC)2.

A metal-organic framework, Cu(3)(BTC)(2), was synthesized and applied as an electro-responsive electrorheological material dispersed in insulating oil. Powder of crystalline Cu(3)(BTC)(2) exhibited excellent chain-like structures and controllable rheological properties in an applied electric field.

Electrorheology of graphene oxide.

Novel polarizable graphene oxide (GO) particles with oxidized groups on their edge and basal planes were prepared by a modified Hummers method, and their electro-responsive electrorheological (ER) characteristics when dispersed in silicone oil were examined with and without an electric field applied. The fibrillation phenomenon of this GO-based electro-responsive fluid was also observed via an optical microscope under an applied electric field. Both flow curves and dielectric spectra of the ER fluid were measured using a rotational rheometer and a LCR meter, respectively. Its viscoelastic properties of both storage and loss moduli were also examined using a vertical oscillation rheometer equipped with a high voltage generator, finding that the GO-based smart ER system behaves as a viscoelastic material under an applied electric field.