Surface hydration and its effect on fluorinated SAM formation on SiO2 surfaces

Substrate hydration is demonstrated to be crucial to film quality during self-assembled (SA) film deposition of tridecafluoro-1,1,2,2,-tetrahydrooctyltrichlorosilane (FOTS) from the vapor phase. The surface hydration was studied by thermogravimetric analysis, and a model was developed to predict the conditions necessary to desorb all of the water adsorbed on a fused silica surface without significantly altering the concentration of the surface hydroxyl groups. The nature of the SA film was investigated as a function of the degree of rehydration of the dehydrated silica surface. The wettability and microstructure of the SA films were examined by water contact angle, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy. There is an optimum degree of substrate hydration, on the order of 1-1.2 monolayers of adsorbed water, required to produce a dense, durable and uniform FOTS film with high water repellency and a smooth surface.     

Poling and crosslinking processes in NLO polymers

A series of photocrosslinkable polymers bearing hyperpolarizable side chain chromophores was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation (SHG). Photoinitiation allowed for control of the onset of curing. Crosslinking was monitored by infrared spectroscopy and optimal conversion was achieved by applying a slow temperature ramp during exposure. The ultimate stability of the poled polymers was directly related to the number of crosslinking substituents that were attached to the chromophore pendant group. With two reactive groups per chromophore significant SHG was retained at temperatures above the initial polymer glass transition temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2769–2775     

ETUDE STRUCTURALE DE QUELQUES SPIROPHOSPHORANES A LIAISON P–C EXOCYCLIQUE

Abstract

The PMR spectra of some spirophosphorans containing the P–C bond are analysed. The results allow us to determine the stereochemistry of these compounds (conformation, stereoisomerism).

Le spectre de RMP de quelques spirophosphoranes à liaison P–C est analysé. Les résultats sont utilisés pour préciser la stéréochimie de ces composés (conformation, stéréoisomérie).     

Polymeric cross-linked surface treatments for controlling block copolymer orientation in thin films

The orientation of cylinder-forming poly(styrene-block-methyl methacrylate) [P(S-b-MMA)] was investigated on two sets of polymeric surface treatments: 10 para-substituted polystyrene derivatives with <10 mol % poly(4-vinylbenzyl azide) and a series of poly(styrene-random-4-vinylbenzyl azide) [P(S-r-VBzAz)] copolymers with 5-100 mol % poly(4-vinylbenzyl azide). The copolymers were spin-coated to form thin films and then cross-linked by heating. The resulting films exhibited a range of surface tensions from 21 to 45 dyn/cm. Perpendicular orientation of P(S-b-MMA) cylinders was achieved with poly(p-bromostyrene) and all the [P(S-r-VBzAz)] copolymer surface treatments, most notably the homopolymer of poly(4-vinylbenzyl azide). Films made from these simple copolymers are as effective as random terpolymer alignment layers commonly made from both block monomers and a cross-linkable monomer.     

A value for partially defined cooperative games

The Shapley value provides a method, which satisfies certain desirable axioms, of allocating benefits to the players of a cooperative game. When there aren players andn is large, the Shapley value requires a large amount of accounting because the number of coalitions grows exponentially withn. This paper proposes a modified value that shares some of the axiomatic properties of the Shapley value yet allows the consideration of games that are defined only for certain coalitions. Two different axiom systems are shown to determine the same modified value uniquely.     

Pulsewidth and interpulse jitter measurements of a passively mode-locked ring CW dye laser

Pulsewidth and jitter measurements have been carried out on a passively mode-locked Rhodamine 6G CW ring dye laser using the SHG autocorrelation technique and a synchroscan streak camera respectively. The pulse durations were measured to be ≈0.18 ps and the cumulative long-term jitter was deduced to be subpicosecond.