On the physical adsorption of gases on carbon materials from molecular simulation

In this paper we present a series of work covering a range of aspects relating molecular simulation to experiment. The importance of surface mediation type effects to the adsorption of simple and complex gases is demonstrated. Coupled with the adsorption of simple gases is their projection area when used for surface area determination. The pressure dependence of a projection area is demonstrated for argon at 77 and 87.3 K. A simple model is used to account for the degree of graphitisation of a surface is demonstrated and used to account for the isosteric heat behaviour of non-graphitised carbon blacks. Turning from surfaces to porous solids, an alternative treatment of experiment data (either sub or super critical) is presented that avoids the ambiguity of excess amounts adsorbed. Using this method one is able to obtain pore size distributions and amounts adsorbed without relying on such things as helium expansion volumes. Since this type of method is usually applied to composite solids we also demonstrate the correct method for calculating the heat of adsorption using independent sets of simulations. The final topic covered in this paper is an example of the information that can be gained from the heat capacity of an adsorbed phase.     

Pore size distributions in low‐k dielectric thin films from X‐ray porosimetry

X‐ray reflectivity has been used to determine the mass uptake of probe molecules in porous thin films supported on thick silicon wafers. The adsorption occurs by capillary condensation when the films are exposed to probe vapor at controlled partial vapor pressures. The probe solvent partial pressure was varied by mixing saturated air and dry air at constant temperature or by changing sample temperature at a constant vapor concentration. Pore size distribution in the films can be calculated from the probe uptake with typical porosimetric approaches such as the application of the Kelvin equation to convert partial pressure into pore size. For illustration, the pore size distribution of three different nanoporous thin films, the primary candidate of ultra‐low‐k interlevel dielectrics in the next generation of integrated circuit chips, was determined with this technique. These samples represent different generations of low‐k dielectrics developed by industry. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2170–2177, 2002     

Studies on the porous structure of di(methacryloyloxymethyl) naphthalene-divinylbenzene copolymers by inverse exclusion chromatography

Summary Using inverse exclusion chromatography the porous structure of the copolymers of di(methacryloyloxymethyl)naphthalenes and divinylbenzene was investigated.In order to determine the pore size distributions of the copolymers, toluene, alkylphenones, phthalates and polystyrene standards were used as the probes.The measurements proved that the existence of micropores depend on the method of copolymerization. The copolymers obtained by suspension and emulsion methods are more or less microporous, but the copolymer prepared by thermal polymerization in mass does not include micropores in its internal structure.     

化学蒸气沉积硅氧化合物调变HZSM－5沸石的研究

本文研究了正硅酸乙酯分别在无胺法和有胺法制得的ＨＺＳＭ－５沸石上的沉积过程，并用吸附，ＮＨ３－ＴＰＤ及异丙醇探针反应等手段表征了沉积后的样品，发现沉积仅在外表面上进行，可使孔口变小但不影响孔道内性质，显示有对于二甲苯分子的择形吸附能力，且在甲苯甲醇烷基化反应和二甲苯异构化反应中表现出良好的择形催化性能．     

Influence of target surface degradation on the properties of r.f. magnetron‐sputtered calcium phosphate coatings

This paper reports a detailed study of how repeated r.f. magnetron sputtering from a hydroxyapatite (HA) powder target affects the nature and reproducibility of a sequential series of thin‐film coatings deposited onto Ti6Al4V substrates. An evaluation of the effective lifespan of the HA sputter targets and the reproducibility of the calcium phosphate (CaP) coatings produced from them has been made from Fourier transform infrared spectroscopy, XPS and, as appropriate, atomic force microscopy and SEM/energy dispersive x‐ray analyses. The annulus region of the target surface, from which sputtering under r.f. magnetron conditions normally occurs, showed severe surface degradation after only one deposition run, as indicated by significant PO₄^3? and OH^? depletion. This deterioration continued after each subsequent deposition cycle but to a much lesser extent than that observed in the initial sputtering period. The layers produced from all of the sputter runs contained the expected Ca²⁺ and PO₄^3? species characteristic of a CaP system but were OH^? deficient in the as‐deposited state. However, the chemical and morphological properties of the coatings did not change significantly until after the third consecutive sputter cycle. Hence, these data indicate that, even though a significant level of degradation of the HA target occurs at the outset of the sputtering procedure, the general plasma conditions employed here have a dominant influence on the coating properties until a critical degradation condition is met. As such, the compacted HA powder targets of interest can have a life‐cycle greater than single usage without detriment to the chemistry and morphology of the coatings produced from them. Copyright © 2003 John Wiley & Sons, Ltd.     

氧化钇粒度控制与测定

用氨水或碳酸氢铵与氯化钇溶液反应生成沉淀，煅烧沉淀制备了D50为0．45μmt 2-10μm的各种粒径的氧化钇粉末。分别采用Coulter MultisizerⅡ和90Plus粒度仪测定微米和亚微米级氧化钇粉体粒度，研究了分散剂，待测样品量，分散时间等因素对亚微米级氧化钇粉体粒度测量精度的影响。     

Effect of NaOH and NaCl on the disodiumn-decane phosphonate micellar aggregation number

The diffusion coefficient of disodiumn-decane phosphonate micelles was studied by polarography at 25°C in NaCl and in NaOH solutions, and the size and aggregation number of the micelles was computed as a function of Na⁺ concentration. All other conditions being equal, the addition of NaCl produces micelles with an aggregation number one order of magnitude larger than the NaOH addition. This is due to the increase of the effective charge per micellized head group produced by the reaction of OH- with the hydrolized head groups which are mainly present as-PO₃H- in the micellar Stern layer.     

Physico-chemical characterization of nanofiltration membranes.

This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly.     

Spectral regions selection to improve prediction ability of PLS models by changeable size moving window partial least squares and searching combination moving window partial least squares

Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions.     

On-column injection onto capillary columns. Part 2: Study of sampling conditions; practical recommendations

During one year continuous use of on-column injection, the typical advantages described in our first report have fully been confirmed. In addition the analysis of large sample volumes has proved promising. Only minor modifications have been applied to the on-column injector device. Broad evidence has been gathered showing that full separation efficiency of the capillary columns after on-column injection is attained only when cold trapping or the solvent effect, as band shortening mechanisms, are working- While, under the conditions of on-column injection, cold trapping is less efficient than with other injection techniques, the opposite holds true for the solvent effect. Compared with splitless injection, the danger of excessive solvent condensation on the column is increased. A working rule is presented for establishing the optimal chromatographic conditions for handling large sample volumes while ensuring full separation efficiency yet avoiding harm to the column.