硅丙涂料的现状及发展趋势

介绍了硅丙涂料在国内外市场的生产及需求现状,指出了硅丙涂料产品的发展方向。     

Surface Chemical Modification of Poly(Methylphenylphosphazene)

Summary The surface reactivity of poly(methylphenylphosphazene), PMPP, and its derivatives containing silane, PMPP-SiH, and alcohol, PMPP-OH, substituents was investigated. These polymers were fabricated into films by casting from THF solutions and reactions were carried out at the interface between solid film samples and solutions. The surface of PMPP was successfully modified by deprotonation under dilute conditions followed by reactions with RMe₂SiCl [where R = CH=CH₂, and H]. While surfaces of PMPP-OH were not readily modified, those containing Si-H groups reacted with oxygen when heated and with carbon tetrachloride. The polymer surfaces were examined by contact angle measurements, attenuated total reflectance infrared spectroscopy (ATR-IR), and scanning electron microscopy (SEM). We dedicate the paper to Christopher W. Allen in recognition of his outstanding contributions to inorganic ring and polymer chemistry.     

STUDY ON PERMEATION OF ACETONE/NITROGEN MIXED GAS THROUGH AL2O3 MICROPOROUS MEMBRANES: MOLECULAR DYNAMICS

In this work, by applying Materials Studio 2.2 software package, molecular dynamics (MD) was performed to investigate the dynamic processes of 1:4 acetone/nitrogen mixed gas permeating through different Al₂O₃ microporous membranes. Three systems were modeled by considering different box lengths, microporous sizes, and textures of Al₂O₃ membranes to compare different permeation behaviors. In each system, initial mixed gas contained 20 acetone molecules and 80 nitrogen molecules, and its density was set to 0.1 g/cm³. Analysis on the concentration profiles of nitrogen molecules (N2) and acetone molecules (Ace) in each system at different sampling times was implemented to discuss the permeation behaviors of smaller N2 and larger Ace. The results showed that adsorption and diffusion occurred synchronously but adsorption was dominant for acetone molecules and that the adsorption on the floor surface of the feed gas region more easily reached equilibrium (local equilibrium) than the diffusion and the adsorption on the ceiling of the initially vacuum region. Furthermore, for nitrogen, adsorption followed diffusion. Higher temperature is in favor of the enrichment of acetone on the floor surface of the feed gas region but against the adsorption of nitrogen. The adsorptive layer was found to be a double-layer with COMPASS force field and to be a monolayer with PCFF force field.     

Enhancement by SO2 of initial activity for selective catalytic reduction of NO with CH3OH over \gamma-alumina

The effect of SO₂ on catalytic activity for NO reduction to N₂ by methanol in excess oxygen over $\gamma$ -alumina has been investigated. SCR activity increased initially upon exposure of a fresh $\gamma$ -alumina catalyst to SO₂ which is attributed to formation of Brønsted acid sites. Longer exposure to SO₂ leads to a decline in catalytic activity to a lower steady-state NO_x reduction activity which is independent of the SO₂ content in the feed gas.     

Analysis of the Thermal Explosion in Systems Porous Reagent–Active Gas–Solid Product

The specific features of dynamics of the thermal explosion in systems porous reagent–active gas–solid product under conditions where the heattransfer and masstransfer regions are separated from the ambient medium are considered. In addition to the competition of heat release and heat removal, the process of initiation of exothermal chemical interaction in these systems under normal pressures depends significantly on conditions of filtration transport of the gaseous reagent. The induction and postinduction periods of the thermal explosion are studied. The theoretical analysis of thermalexplosion issues is supplemented by an experimental study of the process for the porous titanium–nitrogen–titanium nitride system.     

Characterizing electrocatalytic surfaces: Electrochemical and NMR studies of methanol and carbon monoxide on Pt/C

We use cyclic voltammetry (CV) on fuel cell electrodes to elucidate the important differences between adsorbates resulting from carbon monoxide adsorption and methanol adsorption onto commercial Pt/C electrocatalysts in a sulfuric acid electrolyte. Under open circuit conditions, methanol was found to adsorb preferentially onto the Pt sites associated with “strongly bound” hydrogen. The sites associated with “weakly bound” hydrogen adsorbed methanol more slowly. In the case of CO adsorption, which requires no adsorbate dehydrogenation, all adsorption sites showed similar affinity towards the adsorbate. Electrochemical oxidation of the adsorbates derived from both methanol and CO exposure exhibit slower oxidation when the adsorbate is associated with cubic-packed-like sites than from close-packed-steps and other sites. NMR of a ¹³CO-adlayer prepared by electrochemical adsorption from low concentration ¹³CH₃OH shows a lower NMR shift and smaller linewidth than the previously reported values for electrochemically adsorbed ¹³CO gas. These results are interpreted in terms of adsorbate motion on the electrocatalyst surface.     

Axial characterization of catalytic activity in close-coupled lightoff and underfloor catalytic converters

A exhaust system consisting of a close-coupled Pd technology 32 in³ lightoff converter and Pt/Rh technology 170 in³ underfloor converter was vehicle-aged for 56000 miles on a vehicle equipped with a 3.8 l engine. Following this aging, the converters were taken off the vehicle and cut into 1″ thick sections along their axis and characterized for lightoff and warmed-up activity using a laboratory reactor to simulate vehicle exhaust. Each section was also analyzed for the quantity of oil additive poisons (phosphorus and zinc) deposited. Following this initial characterization, the phosphorus and zinc deposits were removed, and the sections were characterized again for lightoff and warmed-up activity. This procedure was used to qualitatively determine the relative contribution of oil additive poisoning and thermal sintering to the total activity deterioration as a function of axial position in the catalyst monoliths.

Analysis of the lightoff converter as taken from the vehicle showed a dramatic axial gradient in the lean and stoichiometric lightoff and warmed-up (600°C) performance for HC, CO and NO_x, with most of the deterioration having taken place in the forward-most 1″ section of the converter, which was consistent with the gradient in the deposition of phosphorus (P) and zinc (Zn) in this converter. Comparison of these data sets with those obtained after removal of the P and Zn poisons indicates that most of the total deterioration of lean HC and CO activity can be attributed to P and Zn poisoning of the forwardmost 1″ section. When tested under stoichiometric conditions, most of the deterioration of HC activity is attributable to P and Zn poisoning, while most of the deterioration of CO and NO_x activity is attributable to thermal deterioration. A similar activity and poison deposition gradient was detected in the underfloor converter, but to a smaller extent.     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

富氢气氛中CO的选择性氧化——碱金属助剂对Pt/γ-Al2O3催化剂性能的影响

研究了碱金属助剂对Pt/γ-Al₂O₃催化剂选择性氧化富氢气氛中CO性能的影响。结果表明，碱金属助剂的引入对Pt/γ-Al₂O₃的催化性能有不同程度的改变，其中添加Na和K后，能明显提高低温下的CO转化率。     

Kinetics of the Initial Stage of Sintering from Shrinkage Data: Simultaneous Determination of Activation Energy and Kinetic Model from a Single Nonisothermal Experiment

A new method for the kinetic analysis of the initial stage of sintering for constant-heating-rate data has been proposed. Unlike all of the methods previously reported in the literature, this new method proposed here allows the simultaneous determination of the activation energy and the kinetic model from a single dilatometric curve recorded under a linear-heating-rate program. The proposed method has been tested with simulated sintering curves and experimental results have been obtained for the sintering of a rutile sample.