Academic collective bargaining, like all collective bargaining, presupposes conflicts between goals of the administration and the academic union. The represented parties on both sides, as well as the general public, typically perceive conflicts in collective bargaining in that way. However, both the administration’s and union’s bargaining teams must substantially resolve internal conflicts among the teams‘ own represented parties before the teams can hope to achieve an acceptable collective-bargaining agreement (i.e., a binding contract). After briefly addressing the very real strengths of academic unions in collective bargaining, we will at greater length explain the origin, nature, and usually imperfect resolution of conflicts arising within an academic union.

The effects of nanoparticles size and surface content of pure silica and in complex fumed metal and metalloid oxides (FMO) on the infrared (IR) spectra in the range of Si-O-Si asymmetric stretching vibrations, were analyzed. Correlation functions were obtained linking the integral intensity of a band at v(siosi) approximate to -1200 cm(-1) (w(2), attributed to the surface of silica); or the ratio w(2)/w(1) (w(1) corresponds to contribution at v(siosi) approximate to 1100 cm(-1) attributed to bulk transverse optical (TO) modes) with the average diameter (d) of silica nanoparticles determined from the specific surface area from nitrogen adsorption' isotherms. The results of the IR spectral analyses were compared to Auger electron spectroscopy (AES) results with respect to surface content of silica in complex FMO. The nanoparticulate morphology of FMO analyzed using TEM and SEM images show a relatively broad size distribution of nanoparticles, including core-shell nanoparticles, that can affect the v(siosi) band intensity and position linked to structural features of the silica phase. Thus, the use of the correlation w(2)(d) or w(2)/w(1)(d) functions give appropriate results for the textural characteristics of fumed silicas and the surface content of silica in complex FMO, compared with nitrogen adsorption and AES data, respectively. (C) 2016 Elsevier B.V. All rights reserved.

A variety of unmodified and modified fumed silica A-300 and silica/titania (ST20 and ST76 at 20 and 76 wt.% of titania, respectively) was prepared to analyze features of their interactions with polar and non-polar adsorbates. The materials were studied using nitrogen adsorption-desorption, ethanol evaporation kinetics, infrared (IR) spectroscopy, thermogravimetry (TG), photon correlation spectroscopy, differential scanning calorimetry (DSC), DSC and TG thermoporometry, and quantum chemistry. Changes in surface structure of modified nanooxides with increasing hydrophobization degree ((sic)(MS)) from 20% to 100% have a strong affect on the textural characteristics of the materials and adsorption-desorption of various adsorbates. Confined space effects enhanced due to the location of adsorbates in narrow voids between nanoparticles lead to freezing-melting point depression for bound polar and non-polar adsorbates. The behavior of particles of modified nanooxides in aqueous and water/ethanol media is strongly altered due to enhanced aggregations with increasing value of (sic)(MS). All of these change are non-monotonic functions of (sic)(MS) which affects (i) rearrangement of nanoparticles, (ii) interactions with polar and nonpolar adsorbates, (iii) location of adsorbates in voids of different sizes, (iv) the clustering of adsorbates and formation of nearly bulk structures. (C) 2017 Elsevier B.V. All rights reserved.

Individual and complex fumed nanooxides were studied using high-resolution transmission electron microscopy, X-ray diffraction, ultraviolet-visible (UV-vis) spectroscopy, differential scanning calorimetry, nuclear magnetic resonance spectroscopy, adsorption, desorption (evaporation), and quantum chemical methods. For mixed nanooxides in contrast to simple and small nanoparticles of individual silica or titania, complex core-shell nanoparticles (50-200nm in size) with titania or alumina cores and silica or alumina shells can be destroyed under high-pressure cryogelation (HPCG), mechnochemical activation (MCA) that also affect the structure of aggregates of nanoparticles and agglomerates of aggregates becoming more compacted. This is accompanied by changes in color from white to beige of different tints and changes in the UV-vis spectra in the 300-600nm range, as well as changes in crystalline structure of alumina. Any treatment of 'soft' nanooxides affects the interfacial behavior of polar and nonpolar adsorbates. For some of them, the hysteresis loops become strongly open. Rearrangement of secondary particles affects the freezing-melting point depression. Clusterization of adsorbates bound in pores causes diminution of heat effects during phase transition (freezing, fusion). Freezing point depression and increasing melting point cause significant hysteresis freezing-melting effects for adsorbates bound to oxide nanoparticles. The study shows that complex nanooxides can be more sensitive to external actions than simple nanooxides such as silica. (C) 2016 Elsevier B.V. All rights reserved.

Investigations of interfacial and temperature behaviors of nonpolar and polar adsorbates interacting with individual and complex fumed metal or metalloid oxides (FMO), initial and subjected to various treatments or chemical functionalization and compared to such porous adsorbents as silica gels, precipitated silica, mesoporous ordered silicas, filled polymeric composites, were analyzed. Complex nanooxides include core–shell nanoparticles, CSNP (50–200nm in size) with titania or alumina cores and silica or alumina shells in contrast to simple and smaller nanoparticles of individual FMO. CSNP could be destroyed under high-pressure cryogelation (HPCG) or mechanochemical activation (MCA). These treatments affect the structure of aggregates of nanoparticles and agglomerates of aggregates, resulting in their becoming more compacted. The analysis shows that complex FMO could be more sensitive to external actions than simple nanooxides such as fumed silica. Any treatment of ‘soft’ FMO affects the interfacial and temperature behaviors of polar and nonpolar adsorbates. Rearrangement of secondary particles and surface functionalization affects the freezing–melting point depression of adsorbates. For some adsorbates, open hysteresis loops became readily apparent in adsorption–desorption isotherms. Clustering of adsorbates bound in textural pores in aggregates of nanoparticles (i.e., voids between nanoparticles in secondary structures) causes reduced changes in enthalpy during phase transitions (freezing, fusion, evaporation). Freezing point depression and melting point elevation cause significant hysteresis freezing–melting effects for adsorbates bound to FMO in the textural pores. Relaxation phenomena for both low- and high-molecular weight adsorbates or filled polymeric composites are affected by the morphology of primary particles, structural organization of secondary particles of differently treated or functionalized FMO, content of adsorbates, co-adsorption order, and temperature.

Amine are known to catalyse silica surface reactions with alkoxy functional organosilanes. In this work, a substoichiometric amount of an aminofunctional silane is bound to the silica surface by reaction with available silanols. This surface bound amine is used to catalyse the reaction of nearby silanols in its vicinity. The result is a bifunctional modified silica surface with two different functional groups intimately mixed at the molecular level. Three types of silicas were modified with a substoichiometric amount of different aminofunctional silanes possessing various structures. These amino-modified silica surfaces were then exposed to a relatively unreactive alkylsilane that requires the presence of an amine for catalysis of the surface reaction. Select materials were characterized by FTIR, TGA, as well as Si-29 and C-13 solid state NMR. Elemental analysis data was obtained for all materials after aminosilane reactions and after alkylsilane reaction, with and without the presence of surface bound aminosilane present, for quantitative analysis. Each surface bound aminosilane catalyses the reaction of approximately one alkylsilane. An aminosilane that is bound with one bond to the surface catalyses a greater number of alklylsilanes per aminosilane. Surface modified aminosilanes on nanoparticulate fumed silica on average catalyse a greater number of alkylsilanes compared to silica gels. This is the first report demonstrating the feasibility of using a surface bound aminosilane as a catalyst to synthesize intimately mixed bifunctional silica surfaces. (C) 2014 Elsevier B.V. All rights reserved.

Unmodified pyrogenic silica PS300 and partially silylated nanosilica samples at a degree of substitution of surface silanols by trimethylsilyl (TMS) groups Θ(TMS)=27.2% and 37.2% were studied to elucidate features of the interfacial behavior of water adsorbed alone, or co-adsorbed with methane, hydrogen, or trifluoroacetic acid (TFAA). In the aqueous suspension modified PS300 at Θ(TMS)=37.2% forms aggregates of 50-200 nm in size and can bind significant amounts of water (up to ∼5 g/g). Only 0.5 g/g of this water is strongly bound, while the major fraction of water is weakly bound. The presence of surface TMS groups causes the appearance of weakly associated water (WAW) at the interfaces. The adsorption of methane and hydrogen onto TMS-nanosilica with pre-adsorbed water (hydration degree h=0.05 or 0.005 g/g) increases with increasing temperature. In weakly polar CDCl3 medium, interfacial water exists in strongly (SAW, chemical shift δ(H)=4-5 ppm) and weakly (δ(H)=1-2 ppm) associated states, as well as strongly (changes in the Gibbs free energy -ΔG>0.5-0.8 kJ/mol) and weakly (-ΔG<0.5-0.8 kJ/mol) bound states. WAW does not dissolve TFAA but some fraction of SAW bound to TMS-nanosilica surface can dissolve TFAA.

Silica cryogels (cryosilicas) in a powder state were synthesized with different concentrations of fumed silica A-300 (CA-300 = 5-20 wt%), sonicated in aqueous suspension, then frozen at -14 degrees C at different pressures in a high-pressure stainless steel reactor (a freezing bomb), and dried in air at room temperature. To analyze the effects of low temperature and high pressure, samples were also prepared at -14 degrees C or room temperature and standard pressure. The structural and adsorption properties of the powder materials were studied using nitrogen adsorption, high-resolution transmission electron microscopy, infrared spectroscopy, thermogravimetry, low-temperature H-1 NMR spectroscopy and thermally stimulated depolarization current. The structural, textural, adsorption and relaxation characteristics of high-pressure cryogel hydrogels and related dried powders are strongly dependent on the silica content in aqueous suspensions frozen at 1450 or 1000 atm and then dried. The largest changes are found with CA-300 = 20 wt% which are analyzed with respect to the interfacial behavior of nonpolar, weakly polar and polar adsorbates using low temperature H-1 NMR spectroscopy. (C) 2013 Elsevier B.V. All rights reserved.

A series of photocatalysts based on silica (nanoparticulate) supported titania, ceria, and ceria/zirconia were synthesized and characterized by a variety of techniques including surface area measurements, X-ray diffraction, Fourier transform infrared spectroscopy, zeta potential, surface charge density, and photocatalytic behavior toward methylene blue decomposition. Thermal treatment at 600 degrees C increases the anatase content of the titania based catalysts detected by XRD. Changes in the infrared spectra before and after thermal treatment indicate that at low temperature there are more Si-O-Ti bonds than at high temperature. As these bonds break upon heating the SiO2 and TiO2 separate, allowing the TiO2 anatase phase to form. This results in an increased catalytic activity for the thermally treated samples. Nearly all titania based samples exhibit a negative surface charge density at pH 7 (initial pH of photocatalytic studies) which aids adsorption of methylene blue. The crystallinity of ceria and ceria/zirconia based catalysts are in some cases limited, and in others non-existent. Even though the energy band gap (E-g) can be lower for these catalysts than for the titania based catalysts, their photocatalytic properties are inferior. (C) 2012 Elsevier B.V. All rights reserved.

To analyze the influence of silica surface modification and confined space effects on specific interactions of divalent and trivalent metal cations with surface functionalities, three different high surface area silicas with different pore size distributions were modified with the following organosilanes: 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(trimethoxysilylpropyl)diethylenetriamine, N-(triethoxysilylpropyl)ethylenediaminetriacetic acid (EDTrA), and 3-(2,4-dinitrophenylamino)propyltriethoxysilane. The silicas were characterized by N(2) adsorption and reflectance FTIR spectroscopy before and after surface modification. N(2) adsorption and pore size distributions showed an increase in the pore width for all EDTrA-modified silicas, opposite to what occurred with the other organosilanes. Adsorption isotherms of Cd(II), Cr(III), Cu(II), and Sr(II) obtained from aqueous solutions were compared and analyzed by silica type, organosilane functional group, and metal adsorbed. Reflectance FTIR spectroscopy was used to probe the acetate functionality in EDTrA as a function of adsorbed metal content. A band shift to higher energy for Cr(III) on the wide pore silica studied indicated that the interaction with the acetate groups can be probed in this manner. In general, the wider pore distribution silica provided larger adsorption maxima, whereas the narrower pore distribution silica provided more favorable ΔG because of stronger binding of the cations. Cr(III) and Cu(II) exhibited larger adsorption maxima compared to Cd(II) and Sr(II), with the grafted organosilanes studied since the first cations have a greater charge/radius ratio than the second ones that provide a greater binding energy.

Co-adsorption of water and methane onto fumed (A-300, A-380) and micro/mesoporous (Gasil 200DF) silicas was studied. FTIR and (1)H NMR spectroscopy with layer-by-layer freezing-out of bound water were used at different levels of hydration (h = 0.005-1.0 g of water per gram of silica). Methane adsorption was largest (1-2 wt% at T < 280 K) for nanosilica A-300 (S(BET) = 337 m(2)/g) at hydration h = 0.1 g of water per gram of silica for a non-equilibrated system. This sample was characterised by a large amount of weakly associated water (delta(H) approximate to 1 ppm), and maximal clustering of all bound water. These conditions provide the increased microporosity necessary for enhanced methane adsorption. Heating and subsequent wetting, or long equilibration of nanosilica, decreased the adsorption of methane. The adsorption of methane on silica 200DF decreased with increasing amounts of pre-adsorbed water, characterised by significant associativity (delta(H) approximate to 5 ppm) at h >= 0.005 g/g. (C) 2011 Elsevier B.V. All rights reserved.

The new ligand 4-PyCH(2)OCS(2)Na, that combines two different donor groups in one molecule (a soft -CS(2)(-) group and a hard pyridine moiety), has been synthesized. The ligand coordinates to a [(bipy)Re(CO)(3)](+) center in a monodentate fashion through one of its soft sulfur atoms, leaving the hard pyridine terminus free for further coordination chemistry. Using a Ni(II) dithiophosphonate linker, the heterometallic {[CH(3)OCH(2)CH(2)OP(An)S(2)](2)Ni}[4-PyCH(2)OCS(2)Re(bipy)(CO)(3)](2) complex is obtained, through the coordination of two pyridine groups to the Ni(II) center. This simple, high-yield stepwise strategy toward heterometallic complexes could be easily transferable to other 1,1-dithiolate ligands and used in combination with a large variety of luminescent metallic systems.

The reaction between (3-aminopropyl)dimethylmethoxysilane (APDMS) with silica and silsesquioxane 3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-ol was studied in hexane and tetrahydrofuran (THF) using experimental (reaction kinetics, FTIR) and quantum chemistry methods. In hexane at temperatures above 245 K, the reaction rate decreases with increasing temperature due to a reduction of prereaction complex formation at higher temperature. Below 245 K the reaction itself is rate limiting, resulting in a reaction rate decrease with decreasing temperature. The reaction occurs much faster in hexane than in THF in part because of stronger competitive effects of the O-containing polar solvent with the formation of APDMS/silsesquioxane prereaction complexes due to hydrogen bonding. Analysis of the experimental data and computational results suggest that the catalytic reaction is second-order with respect to APDMS, the second APDMS molecule plays the role of catalyst. Estimation of the activation energy using dynamic calculations give results much more in agreement with experiment than nondynamic calculations, since the limiting H(+) transfer stage occurs so quickly (approximately 15 fs) that displacements of other atoms are insignificant to the activation energy.