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.     

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.     

Storage of molecular hydrogen into ZSM-5 zeolite in the ambient atmosphere by the sealing of the micropore outlet

The storage of molecular hydrogen into ZSM-5 zeolite in the ambient atmosphere was examined by hydrogen filling into the micropore and the following sealing of the micropore outlet to prevent the release of hydrogen to the outside. The surface grafting of 1,4-bis(hydroxydimethylsilyl)benzene onto ZSM-5 zeolite was applied to the sealing of the micropore outlet. Pressurized hydrogen (10 MPa) was filled into the micropore of ZSM-5 at liquid nitrogen temperature (−196 °C), and then the sample was heated at 150 °C for forming strong binding between the zeolite surface and the disilane compound under the hydrogen pressure. The hydrogen sorption isotherm at −196 °C showed that the adsorption of hydrogen onto the disilane-grafted ZSM-5 thus obtained was reduced to less than 20% from the original ZSM-5. The remarkable hysteresis between the adsorption and desorption branches of the isotherm indicated that the kinetic trap of hydrogen occurred by the narrowed outlets of the micropores of ZSM-5 with the disilane compound. Even after exposing the disilane-grafted ZSM-5 to the atmosphere over a few months, hydrogen could be discharged by heating over 150 °C. This result demonstrated that molecular hydrogen was successfully stored into ZSM-5 zeolite in the ambient atmosphere for a long time.     

Large area deposition of boron doped nano-crystalline diamond films at low temperatures using microwave plasma enhanced chemical vapour deposition with linear antenna delivery

We report on the preparation and characterisation of boron (B) doped nano-crystalline diamond (B-NCD) layers grown over large areas (up to 50 cm × 30 cm) and at low substrate temperatures (< 650 °C) using microwave plasma enhanced linear antenna chemical vapour deposition apparatus (MW-LA-PECVD). B-NCD layers were grown in H₂/CH₄/CO₂ and H₂/CH₄ gas mixtures with added trimethylboron (TMB). Layers with thicknesses of 150 nm to 1 μm have been prepared with B/C ratios up to 15000 ppm over a range of CO₂/CH₄ ratios to study the effect of oxygen (O) on the incorporation rate of B into the solid phase and the effect on the quality of the B-NCD with respect to sp³/sp² ratio. Experimental results show the reduction of boron acceptor concentration with increasing CO₂ concentration. Higher sp³/sp² ratios were measured by Raman spectroscopy with increasing TMB concentration in the gas phase without CO₂. Incorporation of high concentrations of B (up to 1.75 × 10²¹ cm³) in the solid is demonstrated as measured by neutron depth profiling, Hall effect and spectroscopic ellipsometry.     

Luminescence at 2.8 μm: Er3+-doped chalcogenide micro-waveguide

This paper reports the fabrication of luminescent optical rib/ridge waveguides made of erbium doped Ga-Ge-Sb-S films deposited by RF magnetron sputtering. Several fluorescence emissions of Er³⁺ ions from the visible to the middle infrared spectral domain were clearly observed within the films. The study of the ⁴I_13/2 level lifetime enabled development of a suitable annealing treatment of the films to reach the value of the bulk counterpart while the variation in surface roughness was limited, thus ensuring reasonable optical losses (0.7–0.9 dB/cm). Amplification experiments were carried out at 1.54 μm leading to complete characterization of the erbium-doped micro-waveguide with ∼3.4 dB/cm on/off gain. A demonstration of mid-IR photoluminescence from Er³⁺-doped chalcogenide micro-waveguide was recorded at ∼2.76 μm. The multi-luminescence from the visible to mid-IR generated using erbium doped chalcogenide waveguiding micro-structures might find easy-to-use applications concerning telecommunication technologies or on-chip optical sensors for which luminescent sources or amplifiers operating at different wavelengths are required.     

High efficiency panchromatic photopolymer recording material for holographic data storage systems

Studies carried out to gauge the potential of a metal-ion doped panchromatic photopolymer recording material for application in real-time holographic data storage is presented. The photopolymer films are spin coated on glass plates to ensure better surface uniformity. Volume holographic transmission gratings with peak diffraction efficiency of 80% could be stored in the photopolymer films of 100 μm thickness. An efficiency of 70% is achievable even for gratings recorded with exposure energy as low as 10 mJ/cm². A checkerboard pattern data page recorded in the photopolymer film using a defocused 4-f recording geometry could be reconstructed with good image quality. The experimental results illustrate the competency of the developed photopolymer for holographic data storage applications.     

Reversible Amorphous‐to‐Amorphous Transitions in Chalcogenide Films: Correlating Changes in Structure and Optical Properties

Structural transitions in materials are accompanied by appreciable and exploitable changes in physical‐chemical properties. Whereas reversible optically‐driven atomistic changes in crystal‐to‐amorphous transitions are generally known and exploited in applications, the nature of the corresponding polyamorphic transitions between two structurally distinct meta‐stable amorphous phases is an unexplored theme. Direct experimental evidence is reported for the nature of the atomistic changes during fully reversible amorphous‐to‐amorphous switching between two individual states in the non‐crystalline As₅₀Se₅₀ films prepared by pulsed‐laser deposition and consequent changes in optical properties. Combination of surface sensitive X‐ray photoelectron spectroscopy and spectroscopic ellipsometry show that the near‐bandgap energy illumination and annealing induce reversible switching in the material's structure by local bonding rearrangements. This is accompanied by switching in refractive index between two well‐defined states. Exploiting the pluralism of distinct structural states in a disordered solid can provide new insights into the data storage in emerging optical memory and photonic applications.     

Nonlinear optoelectronic materials formed by push–pull (bi)thiophene derivatives functionalized with di(tri)cyanovinyl acceptor groups

Novel nonlinear optical (NLO) materials based on six novel NLO chromophores featuring di(tri)cyanovinyl acceptor linked to (bi)thiophene heterocyclic donor system were fabricated for the first time in polymethyl methacrylate matrices with a 1,064 nm laser working in the 20 ns time pulse regime. Absorption spectra and DFT calculations were also done. This multidisciplinary study showed that tayloring of the optical (linear and nonlinear) properties in the desired direction can be achieved by increasing the length of the π-conjugated heterocyclic system (thiophene vs. bithiophene), the strength of the electron donor groups (H → MeO/EtO → Et₂N) as well as the strength of the electron acceptor moieties (dicyanovinyl vs. tricyanovinyl, two vs. three electron withdrawing cyano groups). Due to the relatively high and tunable second-order susceptibilities (0.08–6.45 pm/V at wavelength 1,064 nm), the studied push–pull chromophores can be denoted as promising second-order NLO chromophores.     

Effect of arc characteristics on the properties of large size diamond wafer prepared by DC arc plasma jet CVD

Diamond wafer with 100 mm in diameter and 1 mm in thickness was prepared by DC arc plasma jet CVD. The area arc distribution above the surface space of substrate, consisting of arc center, arc main and arc edge, directly determined the quality and homogeneity of diamond wafer. As the distance to the central area increased, the crystal size of diamond increased firstly and then decreased. Meanwhile, “dark feature” texture quantity of polished diamond film corresponding to arc main was lower than that corresponding to arc center and arc edge. XRD results showed the ratio of I₍₂₂₀₎/I₍₁₁₁₎ of diamond films increased from edge to center gradually. The intrinsic stress of diamond film corresponding to arc main was greater than the other two areas according to the Raman spectrum, and the highest transmittance in the 10.6 micron wavelength was obtained in the area corresponding to arc main by Fourier infrared. The difference of fracture strength in three areas was less than 20 MPa, which reveals the arc characteristics have less effect on fracture strength.     

Interaction of zinc oxide with bismuth oxide

The lattice parameters of polycrystalline ZnO in mixtures of ZnO-Bi₂O₃ and their dependence on Bi₂O₃-concentration were determined. Simultaneously the influence of ZnO presence on the origin of various modifications of Bi₂O₃ was observed. On the grounds of the measured decrease of the elementary cell volume the supposition about the interaction of Zn-intersititals with overstoichiometric oxygen atoms in Bi₂O₃ was accepted. In accordance with this idea the changes of free carrier concentration of samples ZnO+5 mol% Bi₂O₃ in the dependence on annealing temperature were found.