Convective boiling in a parallel microchannel heat sink with a diverging cross section and artificial nucleation sites

To develop a highly stable microchannel heat sink for boiling heat transfer, three types of diverging microchannels (Type 1, Type 2 and Type 3) were designed to experimentally investigate the effect of different distributions of artificial nucleation sites (ANS) on the enhancement of flow boiling heat transfer, in 10 parallel diverging microchannels with a mean hydraulic diameter of 120 μm. Water was used as the working fluid with mass flux, based on the mean cross section area, ranging from 99 to 297 kg/m² s. The Type-1 system did not contain any ANS; the Type-2 system contained ANS distributed uniformly along the downstream half of the channel; and the Type-3 system contained ANS distributed uniformly along the entire channel. The ANS are laser-etched pits on the bottom wall of the channel and have a mouth diameter of approximately 20-22 μm, as indicted by the heterogeneous nucleation theory. The results of the present study reveal that the presence of ANS for flow boiling in parallel diverging microchannels significantly reduces the wall superheat and enhances the boiling heat transfer performance. The Type-3 system shows the best boiling heat transfer performance.     

How to count strong adsorption sites by gas chromatography?

Summary A simple gas chromatographic method is presented for the determination of the quantity of the strongest adsorption sites on an adsorbent's surface. The method consists of the blockage of the sites with quasi-irreversibly adsorbed, known amount of a strongly interacting compound and subsequent measuring of the retention of a hydrocarbon during the presence of the blocking compound in the column. Heterogeneity of chromatographic grade silicas is investigated with this method.     

Silica surface controversies,strong adsorption sites,their blockage and removal. Part II

Summary In this second part of the review heterogeneity of the silica surface is described and evidence is presented for the existence of a low population of strong adsorption sites. Methods of detection and determination of these strongly interacting sites are discussed. The last part of the review is devoted to the suppression of unwanted adsorption activity. Methods of blockage and special methods for the preparation of HPLC packings are described.     

Preparation and spectroscopic characterization of surface‐enriched (with active sites) polymer‐supported phase‐transfer catalysts and their efficiency in organic addition reactions: A kinetic study

We prepared two batches of surface‐enriched (with active sites) polymer‐supported phase‐transfer catalysts (SE‐PSPTC) by fixing the crosslinking monomer divinylbenzene (DVB) at 2% (first batch) and 6% (second batch) through a free‐radical suspension copolymerization method with vinylbenzyl chloride (VBC; 25%) as a functionality and with styrene (St) as a supporting monomer, followed by the quaternization of the resulting terpolymer beads with triethylamine. The enrichment of the active sites on the surfaces of the beads was accomplished by a surface‐grafting technique through the delayed addition of the functional monomer (VBC) to the partially polymerized copolymer beads of poly(St/DVB). To bring the active sites fully onto the surfaces, we prepared six different types of terpolymer beads in each batch by varying the partial polymerization time (PPT) of St/DVB—0 h [0 VBC (conventional)], 3 h (3 VBC), 6 h (6 VBC), 9 h (9 VBC), 12 h (12 VBC), and 15 h (15 VBC)—and then gradually adding the functional monomer (VBC) to the partially polymerized poly(St/DVB) system. The resulting terpolymer beads, containing different concentrations of pendant benzyl chloride (? CH₂Cl) on the surface in each batch, underwent facile quaternization [? CH₂N⁺(C₂H₅)₃Cl^?] with an increase in the PPT of St/DVB and remained constant at 12 VBC and 15 VBC. To asses the superiority of the catalysts according to the surface enrichment of the active sites, particularly between conventional (0 VBC) catalysts and other PPT‐based SE‐PSPTCs, we characterized all the catalysts by estimating the chloride‐ion concentration, by using Fourier transform infrared (FTIR), scanning electron microscopy (SEM), EDAX, and ESCA, and by carrying out the dichlorocarbene addition to olefins. The chloride‐ion concentration by the Volhard method and the peak intensity of the C? N stretching absorbance concentration, that is, the quaternary onium group in the FTIR spectra of both batches, increased with the PPT of St/DVB in both batches of catalysts. In particular, the chloride concentration of a first‐batch catalyst of a representative mesh size (?120 + 140) had a twofold enhancement between the conventional catalyst (0 VBC; 1.88 m equiv g^?1) and 9 VBC/SE‐PSPTC (3.74 m equiv g^?1), although the same amount of the functional monomer was added in both preparations. These results showed the higher enrichment of the active site on the surface of 9 VBC, and the same trend was also maintained for second‐batch catalysts, regardless of the catalyst mesh size. SEM images of both batches showed that there was a higher concentration of nodules [due to the grafting of poly(VBC)] on the surfaces of the beads of 9 VBC/SE‐PSPTC and the aforementioned PPT catalysts than on the surfaces of the conventional catalysts (0 VBCs), which exhibited smooth surfaces (because of the simultaneous addition of all three monomers). This observation confirmed the enrichment of active sites on the surfaces. In the EDAX analysis, up to a depth of 0.5–1 μm, the surface chloride concentration increased from 0 VBC to 9 VBC/SE‐PSPTC and remained constant in 12 VBC and 15 VBC, first‐batch catalysts of a representative mesh size (?120 + 140). The same trend was also observed in second‐batch catalysts, indicating the enrichment of the onium group more on the surface in 9 VBC/SE‐PSPTCs. The ESCA analysis, to a depth of about 20–30Å, proved that the concentration of covalent chloride on the surface had increased from 0 VBC (15%) to 9 VBC/SE‐PSPTCs (29%) and remained constant thereafter in first‐batch catalyst; the trend was the same for second‐batch catalysts, also confirming the strong evidence of surface enrichment of the active sites. Similarly, the rate constants of different olefin addition reactions catalyzed by both batches of catalysts also increased from 0 VBC to 9 VBC and remained constant with 12 VBC and 15 VBC catalysts. The twofold increase of the rate constants, regardless of the olefins, for conventional catalysts to 9 VBC/SE‐PSPTCs confirmed the enrichment of the active sites on the surfaces. All these experimental observations proved that 50% of the active sites were successfully brought out from inside the poly(St/DVB) networks to the exterior surfaces, although same amount of VBC was added for the preparation of all the catalyst types. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 347–364, 2003     

Detitanation of MgCl2‐supported Ziegler‐Natta catalysts for the study of active sites organization

Thermal treatments under vacuum of conventional supported Ziegler‐Natta precatalysts (MgCl₂/TiCl₄/Dibutylphthalate) were conducted to gradually remove titanium to modify the active sites distribution. Only limited detitanations of precatalysts were achieved paying attention not to chemically alter the internal donor (T < 150 °C). Used in combination with the required cocatalyst and external donor in the propylene slurry polymerization, the modified precatalysts exhibited a drop of activity versus decreasing titanium content but the distributed polymer properties are almost not affected (a slight narrowing of molecular weight distribution was observed). After a titanium chloride secondary impregnation (possibly done in presence of an additional Lewis base), activity resumed but polymer properties are once again unchanged. These findings highlight the difficulty to separate the different families of active sites and lead us to propose a cluster organization of titanium active sites. Active sites are composed of titanium clusters having a size distribution at the precatalyst surface, possessing a critical operating size and operating collectively in polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5461–5470, 2008     

A Mössbauer study of octahedral site symmetries in systems Co x Mn3−x−y Fe y O4 and Ni x Mn3−x−y Fe y O4

A Mössbauer study of cation distribution in systems Co _x Mn_3?x?y Fe _y O₄ and Ni _x Mn_3?x?y Fe _y O₄ has been made. It has been found that in both systems all specimens withy<0.6 value exhibit quadrupole doublets corresponding to site symmetries Fe³⁺(I) and Fe³⁺(II) of octahedral site. As more and more cobalt or nickel is introduced into the matrix the intensity of the inner quadrupole doublet increases while on introducing iron that of the outer quadrupole doublet increases. After a certain concentration of iron the inner doublet starts becoming more intense. It is suggested that this arises possibly from the substitution of cations in the second co-ordination sphere of Fe³⁺(I) and Fe³⁺(II) sites. Fory>0.6 the Mössbauer spectra show relaxation effects.     

A Mössbauer study of hyperfine interaction in the systems Co x Mn3−x−y Fe y O4 and Ni x Mn3−x−y Fe y O4

A Mössbauer study of systems Co _x Mn_3?x?y Fe _y O₄ and Ni _x Mn_3?x?y Fe _y O₄ for values ofx=0·1, 0·5, 1·0 andy ranging from 0·1 to 2·0 in steps of 0·2 have been made. At room temperature samples fory values ranging in between 0·1 to 0·5 exhibit paramagnetic behaviour while all spectra for values ofy between 0·6 to 0·8 show relaxation effects. Well-defined hyperfine Zeeman spectra are observed for all the samples withy>0·8 and resolved in two sextets corresponding to octahedral and tetrahedral site symmetries and a central doublet probably due to the presence of super-paramagnetic particles in the system. The hyperfine field at⁵⁷Fe nucleus reduces with decreasing iron cobalt and nickel concentration. These observations have been explained in terms of site preference of cations and exchange interactions.