Photopolymerization of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester and properties of the cured films

A series of novel waterborne hyperbranched polyurethane acrylates for aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were investigated and used as UV curable oligomers. The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine. The photopolymerization kinetics of these WHPUDs was studied with respect to polymerization rates and unsaturation conversions in the presence of a photoinitiator using differential scanning calorimetry. The polymerization rates of the resins under UV irradiation and the gel contents in the cured films showed an increasing trend with higher concentration of acrylate functionality, which is in favor of the theory of radical chain polymerization. The mechanical and thermal behaviors of UV cured films of aqueous dispersions were evaluated by tensile testing and dynamic mechanical thermal analysis (DMTA). The results of DMTA investigations indicated that the glass transition temperature shifted to higher temperature as the content of the hard segment consisting of IPDI-HEA increased. Moreover, the storage modulus and pendulum hardness also increased with increasing the hard segment content. As the degree of neutralization increased, the T_g and tensile strength decreased, whereas, the elongation at break increased.     

Soft mode dispersion and ‘waterfall’ phenomenon in relaxors revisited

Results of recent inelastic neutron scattering studies of lead-based relaxor ferroelectrics by Gvasaliya et al. [J. Phys.: Condens. Matter 17, 4343 (2005); J. Phys.: Condens. Matter 19, 016219 (2007)] have put in question the existence of the “waterfall” anomaly–an apparent vertical dispersion segment joining the TA and TO branches–observed earlier in low-energy [ξ00] phonon dispersion curves of these materials. In the present article, we review the results of earlier experiments and model calculations together with the outcome of our recent measurements on PMN using the same instrumental set-up as Gvasaliya et al. to conclude that the “waterfall” feature is not an experimental artefact. We also give some hints on a possible explanation of the results of Gvasaliya et al., by exploring the fact that the reported dispersion of the underdamped transverse optic branch follows the longitudinal acoustic (LA) branch dispersion surprisingly closely.     

Magneto-orientational properties of ionically stabilized aqueous dispersions of Ni(OH)2 nanoplatelets

Magnetic and orientational behavior of nickel hydroxide nanoplatelets ionically stabilized in a liquid matrix is studied. Under an applied field the platelets orient their faces normal to its direction. For characterization of the individual behavior of dispersed and non-interacting particles three techniques are used: SAXS, SQUID and magneto-optics. Analysis reveals that nickel hydroxide in a platelet phase is paramagnetic with a pronounced anisotropy of the intrinsic susceptibility, the major component of which (in the direction normal to platelet face) exceeds the minor one by about 25%.     

Graphene oxide: a surfactant or particle?

Graphene oxide is a two-dimensional carbon nanomaterial that has risen to prominence over the last decade as graphenes water-dispersible counterpart. This key feature offers tremendous potential in the formation of waterborne hybrid materials, coatings, membranes and adsorbents that make use of its diverse surface chemistry and extraordinary surface area. However, the fundamental colloidal properties of graphene oxide remain incompletely understood, with conflicting reports on how the material's amphiphilic nature and adsorption at interfaces render it surfactant-like or particle-like in nature. In the present work, recent developments in understanding the bulk and interfacial colloidal properties of graphene oxide are explored in the context of its chemistry and system thermodynamics, giving insight into the fundamental question of whether its aqueous behaviour is most accurately described as particle-like, surfactant-like or indeed something entirely different.     

Poly(ϵ‐caprolactone‐b‐glycolide) and poly(D,L‐lactide‐b‐glycolide) diblock copolyesters: Controlled synthesis,characterization, and colloidal dispersions

Living ω‐aluminum alkoxide poly‐ϵ‐caprolactone and poly‐D,L ‐lactide chains were synthesized by the ring‐opening polymerization of ϵ‐caprolactone (ϵ‐CL) and D,L ‐lactide (D,L ‐LA), respectively, and were used as macroinitiators for glycolide (GA) polymerization in tetrahydrofuran at 40 °C. The P(CL‐b‐GA) and P(LA‐b‐GA) diblock copolymers that formed were fractionated by the use of a selective solvent for each block and were characterized by ¹H NMR spectroscopy and differential scanning calorimetry analysis. The livingness of the operative coordination–insertion mechanism is responsible for the control of the copolyester composition, the length of the blocks, and, ultimately, the thermal behavior. Because of the inherent insolubility of the polyglycolide blocks, microphase separation occurs during the course of the sequential polymerization, resulting in a stable, colloidal, nonaqueous copolymer dispersion, as confirmed by photon correlation spectroscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 294–306, 2001     

Nanofibrilar Polyaniline: Direct Route to Carbon Nanotube Water Dispersions of High Concentration

Water dispersible nanofibrilar polyaniline (NF‐PANI) provides a novel and direct route towards carbon nanotube water dispersions of high concentration. Carrying out the chemical synthesis of NF‐PANI in the presence of carbon nanotubes (CNTs) results in an entirely nanostructured nanofibrilar polyaniline/carbon nanotube (NF‐PANI/CNT) composite material that contains well segregated CNTs partially coated by NF‐PANI. This new approach is simple, fast, and inexpensive, and enables the direct preparation of stable and homogeneous dispersions of the composites in water at concentrations up to 10 mg · mL⁻¹, even for the highest CNT loadings of 50 wt.‐% without the participation of surfactants or stabilizers.

     

Multispeckle diffusing wave spectroscopy of colloidal particles suspended in a random packing of glass spheres

We use a multispeckle diffusing wave spectroscopy (MSDWS) method to study the ensemble-averaged dynamics of the fluctuating speckle pattern when illuminating colloidal particles suspended in a static and opaque porous medium with a coherent light source. Experiments were performed with Brownian latex particles in a random packing of glass spheres. The mixing of the light scattered by the moving colloidal particles and the porous matrix gives rise to a plateau value of the intensity autocorrelation function in the long-waiting-time limit. From the plateau in the correlation function, we can determine the fraction of light scattered from moving particles and estimate the photon mean free path in the colloidal solution. The method opens up promising possibilities to probe the static fraction in semisolid materials.     

Controlled/living heterogeneous radical polymerization in supercritical carbon dioxide

Supercritical carbon dioxide (scCO₂) is an inexpensive and environmentally friendly medium for radical polymerizations. ScCO₂ is suited for heterogeneous controlled/living radical polymerizations (CLRPs), since the monomer, initiator, and control reagents (nitroxide, etc.) are soluble, but the polymer formed is insoluble beyond a critical degree of polymerization (J_crit). The precipitated polymer can continue growing in (only) the particle phase giving living polymer of controlled well‐defined microstructure. The addition of a colloidal stabilizer gives a dispersion polymerization with well‐defined colloidal particles being formed. In recent years, nitroxide‐mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization have all been conducted as heterogeneous polymerizations in scCO₂. This Highlight reviews this recent body of work, and describes the unique characteristics of scCO₂ that allows composite particle formation of unique morphology to be achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3711–3728, 2009     

Rheological investigation of thermal transitions in vesicular dispersion

The thermal behavior of unsonicated dispersions of a double-chained surfactant, Dioctadecyldimethylammonium bromide (DODAB), has been studied over a wide concentration range using DSC and dynamic rheology. All dispersions are characterized by the pre- and main transition peaks at 35 °C and 43 °C, respectively. But, only above 10 mM DODAB, a third endotherm at 52 °C appears which may correspond to the (ULVs + L_α fragments) → MLVs transition. The thermal-induced MLV’s size is proportionally dependent on the concentration. In addition, and in agreement with DSC data, dynamic rheology has proven to be an indirect way to elucidate the structural transitions in these DODAB vesicular dispersions.