Colloidal stability of magnetite/poly(lactic acid) core/shell nanoparticles

In this work, we describe an experimental investigation on the colloidal stability of suspensions of three kinds of particles, including magnetite, poly(lactic acid) (PLA), and composite core/shell colloids formed by a magnetite core surrounded by a PLA shell. The experiments were performed with dilute suspensions, so that recording the optical absorbance with time gives a suitable indication of the aggregation and sedimentation of the suspensions. The method allowed us to distinguish very accurately between the different surface and magnetic forces responsible for the structures acquired by particle aggregates. Thus, the pure PLA suspensions are very sensitive to ionic strength and almost unaffected by pH changes. On the contrary, the stability of magnetite systems is mainly controlled by pH. The effect of vertical magnetic fields on the stability of magnetite and magnetite/PLA suspensions is also investigated. The PLA shell reduces the magnetic responsiveness of magnetite, but it is demonstrated that the mixed particles can also form structures induced by the field, despite their lower magnetization, and they can be considered in magnetically targeted biomedical applications.     

Precision in transient electric birefringence measurements for colloids

Electrically induced birefringence is increasingly used as a fast procedure to characterise the size, shape, polarisation and charge parameters of colloids and their interactions. By considering the optical apparatus generally used, attention is drawn to the significant errors that can arise in such experiments if optical component selection and setting are not critically considered.     

Magnetic alignment of the chiral nematic phase of a cellulose microfibril suspension

Stable suspensions of tunicate cellulose microfibrils were prepared by acid hydrolysis of the cellulosic mantles of tunicin. They formed a chiral nematic phase above a critical concentration. External magnetic fields were applied to the chiral nematic phase in two different manners to control its phase structure. (i) Static magnetic fields ranging 1-28 T were used to align the chiral nematic axis (helical axis) in the field direction. (ii) A rotating magnetic field (5 T, 10 rpm) was applied to unwind the helices and to form a nematic phase. These phenomena were interpreted in terms of the anisotropic diamagnetic susceptibility of the cellulose microfibril. The diamagnetic susceptibility of the microfibril is smaller in the direction parallel (chi( parallel)) to the fiber axis than in the direction perpendicular (chi( perpendicular)) to the fiber axis, that is, chi( parallel) < chi( perpendicular) < 0. Because the helical axis coincides with the direction normal ( perpendicular) to the fiber axis, the helical axis aligned parallel to the applied field. On the other hand, the rotating magnetic field induced the uniaxial alignment of the smallest susceptibility axis, that is, chi( parallel) in the present case, and brought about unwinding of the helices.     

An instrument for measuring the oscillatory electric birefringence properties of polymer solutions

An instrument for measuring the oscillatory electric birefringence properties of synthetic polymer dissolved in organic solvents has been designed and constructed. Novel features of the design include an in situ variable inter-electrode spacing Kerr cell and a double-beam optical train. The accessible frequency range extends from below 1 Hz to at least 100 kHz, with electric fields variable up to approximately 6000 V cm^?1 (peak-to-peak). Measurements are made with a powerful computerized data acquisition and processing system, based on an approach previously used for viscoelastic and oscillatory flow birefringence experiments. Preliminary results on a viscous liquid, Aroclor-1248, indicate that time-temperature superposition holds to reduced frequencies of at least 100 MHz. Comparison with theoretical predictions for rigid rod suspensions suggests that this liquid exhibits relaxation behavior with a time constants of ca. 6 ns at 25.00°C.     

Liquid crystal birefringence for millimeter wave radar

Abstract

Many liquid crystals are found to have relatively high birefringence (Δn) values in the microwave and millimeter wave regions, as calculated from the phase shift induced by their reorientation by magnetic or electric fields. At 30 GHz, Δn values were obtained in the range of 0.08 to 0.18 for eleven liquid crystal mixtures of various types. The most favourable liquid crystal structures for high millimeter wave birefringence are highly conjugated rod-like molecules containing biphenyl, terphenyl, phenylpyrimidine, biphenylpyrimidine, and tolane groups in nematics of positive dielectric anisotropy (Δε). However, other liquid crystal structures including Schiffs base, azoxybenzene, and aromatic ester groups also have substantial birefringence, including nematics with negative and crossover Δε, as well as cholesteric nematics. The Δn varied only slightly at different frequencies of microwave millimeter wave in the 15–94 GHz range. Studies on magnetic and electrical field liquid crystal orientation in specially designed waveguides provide a basis for new types of modulators and scanning array antennae in the millimeter wave region, where more compact liquid crystal modulation media can be used than in the microwave region. These scanners can be used for both sending and receiving radar signals for potentially low cost radar systems.     

Optical anisotropy of a thermotropic liquid-crystalline polymer in transient shear

A rheo-optical apparatus, based on a linear shear rheometer, has been constructed to study the deformation of liquid–crystalline polymers. This apparatus uses optical techniques such as flow birefringence, small-angle light scattering, and optical microscopic image analysis. The rheological responses were simultaneously measured under varying temperatures and deformation conditions. The modified Debye-Bueche equation for scattering, in the nonspherically symmetrical form, was adapted to analyze small-angle light-scattering data. The orientation correlation lengths, determined by this method, reveal the deformation mechanism in nematic melts. Flow birefringence results are in agreement with the proposed mechanism.     

Chiral nematic suspensions of cellulose crystallites; phase separation and magnetic field orientation

Suspensions of rod-like cellulose crystallites of axial ratio ≈ 20-40, prepared by acid hydrolysis of natural cellulose fibres with sulphuric acid, give stable ordered fluids that display well-formed textures and disclinations characteristic of chiral nematic liquid crystalline phases. The critical volume fraction for phase separation of salt-free suspensions is typically 0.03, with a relatively narrow biphasic region. Because of the negative diamagnetic susceptibility of cellulose, the ordered phase becomes oriented in a magnetic field with its chiral nematic axis parallel to the applied field.     

The influence of interparticle surface forces on the coagulation of weakly magnetic mineral ultrafines in a magnetic field

In this paper, it is shown that the coagulation of dispersions of weakly magnetic mineral ultrafines (such as hematite and chromite) in an external magnetic field can be described theoretically by invoking interparticle forces. Essentially, coagulation occurs when the short-range London—van der Waals interactions and the long-range magnetic forces outweigh the stabilizing electric double layer repulsion. From classical colloid chemistry theory, we have calculated the various components of the potential energy for different-sized particles at a series of ionic strengths and magnetic field intensifies. Principles governing the stability of the suspensions were derived and the computations lead to the establishment of criteria which can be used to predict the stability of the suspensions of weakly magnetic oxide mineral ultrafines in a “wet magnetic separation process”.

Experimentally, the magnetic-field induced coagulation of ultrafines of natural hematite and chromite in aqueous suspensions at moderate ionic strength was investigated using a laboratory-scale electromagnetic solenoid. The experimental results relate the coagulation process (as determined by magnetosedimentation analysis) to particle size, slurry pH and the external magnetic field. In the magnetic fields, maximum coagulation occurred near the pH of the point of zero charge (pH_PZC) of the minerals (where the electrostatic double layer repulsion was reduced to a minimum) enabling the particles to enter the “primary minimum” energy sink. In contrast, in cases where the electrostatic repulsion was not suppressed, the long-range magnetic forces enabled coagulation to occur in the “secondary minimum”. This caused the formation of chains which appeared to be relatively stable at enhanced rates of settling. The experimental results could be interpreted from a theoretical analysis of the interparticle forces controlling the process.     

Magnetic alignment of self-assembled anthracene organogel fibers

High magnetic fields are shown to be remarkably effective to orient self-assembled 2,3-bis-n-decyloxyanthracene (DDOA) fibers during organogel preparation. Magnetic orientation of DDOA results in a highly organized material displaying a fiber-orientation order parameter of 0.85, a large linear birefringence, and fluorescence dichroism. The aligned organogel is stable after removal of the magnetic field at room temperature and consists of fibers oriented perpendicular to the magnetic field direction, as shown by scanning electron microscopy. Models for the molecular organization within the gel fibers are discussed upon quantitative analysis of the birefringence. Prospectively, magnetic alignment can be used to improve specific properties of organogel materials.     

Comparison of optical and mechanical limits of linear relaxation behavior in glassy polycarbonate

The decay in birefringence of glassy polycarbonate held at constant extension has been studied at 23°C, in the time-scale range 10–10³ sec, up to about 6% strain. The results show that, under these conditions, the birefringence can be validly expressed as a linear hereditary integral of the strain history up to a relatively high strain level which is about 3.4% for an experimental time-scale of 100 sec. Comparison with previously obtained data on the stress relaxation behavior of the same polymer shows that, other factors remaining constant, mechanical relaxation is linear only up to about 1.1% strain. The earlier onset of mechanical nonlinearity is discussed and it is suggested that the mechanical relaxation spectrum is richer than the optical spectrum in relatively long relaxation times, corresponding to relatively slow molecular motions. It is further suggested that these slow molecular motions are accelerated first as the polymer is extended beyond the limit of linear viscoelastic behavior. The observed nonidentity between strain limits for linear mechanical and linear optical behavior is discussed in the light of current practices in photomechanical stress analysis.     

On the theory of birefringence in magnetic fluids

The influence of homogeneous correlations between the positions and orientations of ferroparticles on the effect of light birefringence in magnetic fluids has been studied. It has been demonstrated that, for typical magnetic fluids, the optical effects associated with the homogeneous correlations can be stronger than the effects caused by elongated primary aggregates formed at the stage of ferrofluid synthesis, as well as heterogeneous chains resulting from magnetic attraction between the largest particles of a magnetic fluid.     

Rheo-optical properties of polyethylene films in the nonlinear viscoelastic region

A new apparatus was designed to investigate the dynamic viscoelastic properties of solid polymer materials in the nonlinear viscoelastic region. The apparatus was combined with a birefringence apparatus in such a way that birefringence could be measured simultaneously with stress under oscillatory deformation. The nonlinear viscoelastic behavior of bulk-crystallized high-density polyethylene films was examined. Nonlinearity of mechanical properties became evident around 30°C, while optical properties became markedly nonlinear around 50°C. The nonlinearity of viscoelastic properties changes very little when the films are swollen with tetrachloroethane. It is proposed that disruption of lamellae to crystallites in the drawing process is one of the most important causes of the nonlinear behavior of high-density polyethylene films.     

Interface-induced anisotropy and the nematic glass/gel state in jammed aqueous Laponite suspensions

Aqueous suspensions of Laponite, a system composed of disklike nanoparticles, are found to develop optical birefringence over several days, well after the suspensions solidified because of jamming. The optical anisotropy is particularly enhanced near the air-Laponite suspension interface over length scales of several millimeters, which is beyond 5 orders of magnitude larger than the particle length scale, suggestive of large-scale ordering influenced by the interface. The orientational order increases with time and is always greater for higher concentration of salt, higher concentration of Laponite, and higher temperatures of the suspension. Although weakly birefringent, Laponite suspensions covered by paraffin oil do not show any enhancement in optical anisotropy near the interface compared to that in the bulk. We suggest that the expedited structure formation near the air interface propagating progressively inside the sample is responsible for the observed behavior. We discuss the observed nematic ordering in the context of glass-like and gel-like microstructure associated with aqueous Laponite suspensions.     

Electric dipole moments of particle aggregates in magnetite colloidal solutions in liquid dielectrics

The permanent electric moments and the electric polarizability anisotropy of particle aggregates are determined from the results of measuring the birefringence of a magnetite colloidal solution in kerosene subjected to constant and pulsed electric fields. A possible mechanism of generating an induced dipole moment in the aggregates is analyzed. The moment is characterized by a long relaxation time and, according to the results of optical experiments, is interpreted as permanent. The calculated dipole moments are consistent with the experimental data in the order of magnitude.     

Electric field effect on the nematic-isotropic phase transition

Pulsed electric fields are used to study the influence of a strong field on the nematic-isotropic phase transition for cyanobiphenyl and stilbene-type liquid crystals. Deviation of the electric field-induced optical anisotropy from the Kerr law is observed and it is shown that such electric fields can shift the transition temperature substantially. The induced birefringence and the shift of the transition temperature are measured as a function of the electric field strength. The results are explained qualitatively in the context of the Landau-De Gennes theory with two order parameters. The coefficients of the phenomenological theory are calculated using the simple density functional theory of polar nematics developed in this paper and the results for the shift of the transition temperature are compared with experiment results.     

Magnetic susceptibility tensor anisotropies for a lanthanide ion series in a fixed protein matrix.

The full series of lanthanide ions (except the radioactive promethium and the S-state gadolinium) has been incorporated into the C-terminal calcium binding site of the dicalcium protein calbindin D(9k). A fairly constant coordination environment is maintained throughout the series. At variance with several lanthanide complexes with small chelating ligands investigated in the past, the large protein moiety provides a large number of NMR signals whose hyperfine shifts can be exclusively ascribed to pseudocontact shifts (PCS). The chemical shifts of 1H and 15N backbone and side chain amide NH groups were accurately measured through HSQC experiments. 1097 PCS were estimated from these by subtracting the diamagnetic contributions measured on HSQC spectra of either the 4f(0) lanthanum(III) or the 4f(14) lutetium(III) derivatives and used to define a quality factor for the structure. The differences in diamagnetic chemical shifts between the two diamagnetic blanks were relatively small, although some were not negligible especially for the nuclei closest to the metal center. These differences were used as a tolerance for the PCS. The magnetic susceptibility tensor anisotropies for each paramagnetic lanthanide ion were obtained as the result of the solution structure determination performed by using the NOEs of the cerium(III) derivative and the PCS of all lanthanides simultaneously. This set of reliable magnetic data permits an experimental assessment of Bleaney's theory relative to the magnetic properties for an extended series of lanthanide complexes in solution. All of the obtained tensors show some rhombicity, as could be expected from the lack of symmetry of the protein environment. The directions of the largest magnetic susceptibility component for Ce, Pr, Nd, Sm, Tb, Dy, and Ho and of the smallest magnetic susceptibility component for Eu, Er, Tm, and Yb were found to be all within 15 degrees from their average (within 20 degrees for Sm), confirming the essential similarity of the coordination environment for all lanthanides. Bleaney's theory is in excellent qualitative agreement with the observed pattern of axial anisotropies. Its quantitative agreement is substantially better than that suggested by previous analyses performed on more limited sets of PCS data for small lanthanide complexes, the so-called crystal field parameter varying only within +/-30% from one lanthanide to another. These variations are even smaller (+/-15%) if a reasonable T(-3) correction is taken into consideration. A knowledge of magnetic susceptibility anisotropy properties of lanthanides is essential in determining the self-orienting properties of lanthanide complexes in solution when immersed in magnetic fields.     

Viscoelasticity of suspensions of magnetic particles in a polymer: effect of confinement and external field

We study the suspensions of magnetic particles, the precursor state of magnetic gels and elastomers. We use magnetic particles with a permanent magnetization which is high enough to overcome thermal energy and low enough to guarantee a long live time of the sample. These particles form a space-filling structure at very low volume fractions (approximately 0.5 vol %), which modifies the viscoelastic response of the matrix significantly. In confined geometry the particles form clusters of a size that depends on the sample thickness. Even small external fields induce a strong anisotropy in the mechanical and optical properties of the suspension. The action of the applied magnetic field induces a gel-like response in one direction but leaves the other directions liquidlike. The viscosity is a very sensitive mechanical test for the anisotropy of the material. Light scattering data confirm our mechanical results.     

Optical, dynamic, and electro-optical properties of poly(N-acryloyl-11-aminoundecanoic acid) in solutions

The optical, electro-optical, and dynamic characteristics of poly(N-acryloyl-11-aminoundecanoic acid) in organic solvents and of the sodium salt of its monomer in water were studied via the methods of flow birefringence, equilibrium and nonequilibrium electric birefringence, and dynamic light scattering. It is shown that, in aqueous solutions, the monomer forms coarse particles of both symmetric and asymmetric shapes. The linear dimensions of these particles are estimated from the data of translational and rotational diffusion. Polymer macromolecules in organic solvents feature negative anisotropy of optical polarizability. Contributions of optical microform and macroform effects to the observed flow birefringence are analyzed in detail. The intrinsic optical anisotropy of the monomer unit of the polymer, which correlates well with the corresponding values for comb-shaped polymers of a similar structure, is estimated. It is shown that polymer molecules lack marked intrinsic permanent macromolecular dipoles and that electric birefringence in their solutions is associated with macroscopic induced dipole moments that appear during orientation of the dipole moments of polar groups in side chains of the polymer under application of an electric field.     

Magnetic orientation of 1,3,5-triphenyl-6-oxoverdazyl radical crystals

The magnetic orientation has been studied for paramagnetic organic radical crystals 1,3,5-triphenyl-6-oxoverdazyl and 1,5-di-p-tolyl-3-phenyl-6-oxoverdazyl in magnetic fields of 2-80 kOe at temperatures of 77-343 K. The X-ray diffraction measurement has revealed that the crystals are oriented with the crystallographic c axis perpendicular to the field. The anisotropic diamagnetic susceptibility arising from the benzene rings has been estimated for the crystals along the principal magnetic chi 1, chi 2, and chi 3 axes. (The chi 1 axis is at a small angle to the a axis in the monoclinic ac plane, and the chi 3 axis is along the b axis.) Since the paramagnetic susceptibility originating from the verdazyl ring is isotropic (though a large absolute value), it is shown that the magnetic orientation occurs by the anisotropy of the diamagnetic susceptibility in the crystals. The diamagnetic susceptibility is found to have a relation of chi 2 < chi 1 < chi 3 < 0.     

On the electrical polarization of polymer single crystals in suspension

A model is proposed for the electrical polarization that causes the orientation and, hence, the electric birefringence of a suspension containing single crystals of a poly(ethylene oxide)–polystyrene diblock copolymer or a poly(ethylene oxide) homopolymer. It serves to describe how an electric dipole moment lying in the plane of the single crystal can be induced by protons migrating in poly-(ethylene oxide). The resulting Kerr effect is calculated up to saturating fields, and the observed dispersion of the polarization in high frequency fields is explained as a space charge relaxation phenomenon. The estimated relaxation time agrees satisfactorily with published experimental data.