On the role of hydrophilicity and hydrophobicity in aqueous heterophase polymerization

This paper reports on experimental results of aqueous heterophase polymerizations with monomers of quite different solubility in water ranging from the water-soluble 2-hydroxyethyl methacrylate to lauryl methacrylate with solubility in water of only about 10⁻⁴ mM. A calorimetric study revealed the strong influence of both the hydrophilicity of the monomer and the stirrer speed on the rate of polymerization in the absence of surfactants. In order to obtain maximum latex yield and high efficiency (which is a measure considering colloidal properties, polymerization recipe, and polymerization parameters) the initiator-surfactant combination must be properly chosen in dependence on the hydrophilicity of the monomer. Results are presented for sodium alkyl sulfates or disodium-N-stearoyl-l-glutamate as surfactant and potassium peroxodisulfate, or poly(ethylene glycol)-azo- compounds, or 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonates as initiators.     

Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.     

Comparing emulsion polymerization of methacrylate-monomers with different hydrophilicity

A comprehensive experimental study concerning the influence of various types of initiator-emulsifier systems on emulsion polymerization of methacrylate monomers (2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and butyl methacrylate (BMA)) reveals interesting relations between initiator and surfactant hydrophilicity on the one hand and the hydrophilicity of the monomers on the other hand. For the water-soluble HEMA stable latexes are only obtained if hydrophobic initiators such as 2,2′-azobisisobutyronitrile or dibenzoyl peroxide in combination with alkyl sulfate surfactants with carbon chain lengths greater than 10 or surface active initiators of the 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonate type with alkyl chain lengths greater than 8 are employed. Stable nano size range poly(2-hydroxyethyl methacrylate) (PHEMA) particles have been prepared also by batch emulsion polymerization using ionic surface active initiators (inisurfs). The results clearly show that the formation of stable latex particles requires a proper choice of the initiator-emulsifier system regarding its hydrophilic-hydrophobic balance. The PHEMA particles prepared with surface-active initiators keep their identity and spherical shape even in the dried state whereas in the case of the other initiator-emulsifier systems complete coagulation and coalescence occurs during drying.     

An Interoperable Grid Information System for Integrated Resource Monitoring Based on Virtual Organizations

In many Grid infrastructures different kinds of information services are in use, which utilize different incompatible data structures and interfaces to encode and provide their data. Homogeneous monitoring of these infrastructures with the monitoring data being accessible everywhere independently of the middleware which provided it, is the basis for a consistent status reporting on the Grids’ resources and services. Thus, interoperability or interoperation between the different information services in a heterogeneous Grid infrastructure is required. Monitoring data must contain the identity of the affected Virtual Organization (VO) so that it can be related to the resources and services the VO has allocated to enable VO-specific information provision. This paper describes a distributed architecture for an interoperable information service, which combines data unification and categorization with policies for VO membership, VO resource management and data transformations. This service builds the basis for an integrated and interoperating monitoring of Grids, which provide their data to more than one VO and utilize heterogeneous information services.     

Solid Ink Laser Patterning for High-Resolution Information Labels with Supervised Learning Readout

Tagging, tracking, or validation of products are often facilitated by inkjet-printed optical information labels. However, this requires thorough substrate pretreatment, ink optimization, and often lacks in printing precision/resolution. Herein, a printing method based on laser-driven deposition of solid polymer ink that allows for printing on various substrates without pretreatment is demonstrated. Since the deposition process has a precision of <1 µm, it can introduce the concept of sub-positions with overlapping spots. This enables high-resolution fluorescent labels with comparable spot-to-spot distance of down to 15 µm (444,444 spots cm⁻²) and rapid machine learning-supported readout based on low-resolution fluorescence imaging. Furthermore, the defined thickness of the printed polymer ink spots can be used to fabricate multi-channel information labels. Additional information can be stored in different fluorescence channels or in a hidden topography channel of the label that is independent of the fluorescence.     

Uncertainty propagation in puff-based dispersion models using polynomial chaos

Atmospheric dispersion is a complex nonlinear physical process with numerous uncertainties in model parameters, inputs, source parameters, initial and boundary conditions. Accurate propagation of these uncertainties through the dispersion models is crucial for a reliable prediction of the probability distribution of the states and assessment of risk. A simple three-dimensional Gaussian puff-based dispersion model is used as a test case to study the effect of uncertainties in the model parameters and initial conditions on the output concentration. A polynomial chaos based approach is used to numerically investigate the evolution of the model output uncertainties due to initial condition and parametric uncertainties. The polynomial chaos solution is found to be an accurate approximation to ground truth, established by Monte Carlo simulation, while offering an efficient computational approach for large nonlinear systems with a relatively small number of uncertainties.     

Evidence of the vital role of the pore network on various catalytic conversions of N2O over Fe-silicalite and Fe-SBA-15 with the same iron constitution

Fe-silicalite and Fe-SBA-15 with similar iron content have been characterized by N₂ adsorption, small angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), scanning electron microscopy (SEM), high-resolution transmission electron micrographs (HRTEM), UV–vis–DRS and EPR, and tested in direct N₂O decomposition, N₂O reduction by CO and N₂O-mediated propane oxidative dehydrogenation. Both catalysts contain almost exclusively isolated Fe³⁺ sites of similar concentration and structure, which are, however, stabilized in markedly different pore geometries (intersecting channels of ca. 0.55 nm diameter in Fe-silicalite versus parallel linear pores of ca. 7.5 nm diameter in Fe-SBA-15). This aspect is of vital importance in order to exclusively ascribe different catalytic performances to the environment where the iron species are stabilized. Fe-silicalite revealed to be much more active than Fe-SBA-15 in all reactions studied. This clearly illustrates that the confinement of the iron species in pores of suitable geometry (structure and size) is essential to originate their remarkable catalytic properties. The large pores in ordered mesoporous materials apparently do not generate the required intimate contact between potentially active Fe sites and reactant molecules.     

High optical quality spin-coated polyphenylsiloxane glass thick films on polyethyleneterephtalate and silica substrates

We report a facile route for the preparation of polyphenylsiloxane ((1 − x)PhSiO_3/2–(x)Ph₂SiO_2/2 (x = 0, 0.1, 0.2, 0.3)) glass films from 50 to 150 μm thick. The films were obtained via a multi-step spin-coating process at room temperature using a non-aqueous coating sol where the preformed polyphenylsiloxane is homogeneously dissolved in acetone. The different stages of the spinning process have been described and optimised, and represent an important issue to the preparation of homogeneous films. The thickness of the films (H) coated on silica and polyethyleneterephtalate substrates showed a trend dependency with the sol viscosity (η), H ∝ η^0.37 and H ∝ η^0.41, respectively, making the thickness of the films easy to control. The average surface roughness evaluated to be less than 5 nm and the high optical transmittance (99%) demonstrated the high quality coatings. In addition, the stability of the glass matrix in the solvent makes this method of practical interest for tremendous possibilities in a wide range of applications such as the development microfluidic channels, protective coatings and optical components.