Experimental methods in chemical engineering: X-ray photoelectron spectroscopy-XPS

X\u2010ray photoelectron spectroscopy (XPS) is a quantitative surface analysis technique used to identify the elemental composition, empiricalformula, chemical state, and electronic state of an element. The kinetic energy of the electrons escaping from the material surface irradiated by anx\u2010ray beam produces a spectrum. XPS identifies chemical species and quantifies their content and the interactions between surface species. It isminimally destructive and is sensitive to a depth between 1\u201310 nm. The elemental sensitivity is in the order of 0.1 atomic %. It requires ultra highvacuum (1 7107 12Pa) in the analysis chamber and measurement time varies from minutes to hours per sample depending on the analyte. XPSdates back 50 years ago. New spectrometers, detectors, and variable size photon beams, reduce analysis time and increase spatial resolution. AnXPS bibliometric map of the 10 000 articles indexed by Web of Science[1]identifies five research clusters: (i) nanoparticles, thin films, and surfaces;(ii) catalysis, oxidation, reduction, stability, and oxides; (iii) nanocomposites, graphene, graphite, and electro\u2010chemistry; (iv) photocatalysis,water, visible light, andTiO2; and (v) adsorption, aqueous solutions, and waste water

Dust masses of disks around 8 Brown Dwarfs and Very Low-Mass Stars in Upper Sco OB1 and Ophiuchus

We present the results of ALMA band 7 observations of dust and CO gas in the disks around 7 objects with spectral types ranging between M5.5 and M7.5 in Upper Scorpius OB1, and one M3 star in Ophiuchus. We detect unresolved continuum emission in all but one source, and the $^{12}$CO J=3-2 line in two sources. We constrain the dust and gas content of these systems using a grid of models calculated with the radiative transfer code MCFOST, and find disk dust masses between 0.1 and 1 M$_\oplus$, suggesting that the stellar mass / disk mass correlation can be extrapolated for brown dwarfs with masses as low as 0.05 M$_\odot$. The one disk in Upper Sco in which we detect CO emission, 2MASS J15555600, is also the disk with warmest inner disk as traced by its H - [4.5] photometric color. Using our radiative transfer grid, we extend the correlation between stellar luminosity and mass-averaged disk dust temperature originally derived for stellar mass objects to the brown dwarf regime to $\langle T_{dust} \rangle \approx 22 (L_{*} /L_{\odot})^{0.16} K$, applicable to spectral types of M5 and later. This is slightly shallower than the relation for earlier spectral type objects and yields warmer low-mass disks. The two prescriptions cross at 0.27 L$_\odot$, corresponding to masses between 0.1 and 0.2 M$_\odot$ depending on age.Comment: 9 pages,6 figures, accepted to ApJ on 26/01/201

Catalyst preparation for fluidized bed reactors by spray drying

Spray dried fluidized bed catalysts belong to the Geldart Group A classification and vary between 22 m to 200 m in diameter (1). Binder is either distributed throughout the particle with the active phase or surrounds the active phase as in a core-shell structure (2, 3). We slurried WO3/TiO2 micronized powder (0.2 m to 2 m) with colloidal silica (LUDOX® HS-40) to form a slurry with a mass fraction of 5 % to 20 % solids. The solution entered the top of GB-22 Yamato fluidized bed spray dryer chamber (0.12 m ID) through a two-fluid nozzle and the drying air entered the bottom counter-currently. We varied the feed slurry concentration, binder concentration, slurry and drying air flow rates, two-phase nozzle pressure drop and inlet temperature. Most conditions only produced a very fine powder (Group C, dpm) (Fig. 1a). (Ideally, the particle size should exceed 80 m for laboratory experimental equipment). The small particles were often fully spherical but we also produced large clusters that reached 150 m (Fig. 1b). The high pressure drop through the nozzle and low slurry concentration produced the fine powder. Particles agglomerated in the fluidized bed when we increased the slurry flow rate to the chamber such that the powder had not yet dried sufficiently. Please click Additional Files below to see the full abstract

The Ages of A-Stars I: Interferometric Observations and Age Estimates for Stars in the Ursa Major Moving Group

We have observed and spatially resolved a set of seven A-type stars in the nearby Ursa Major moving group with the Classic, CLIMB, and PAVO beam combiners on the CHARA Array. At least four of these stars have large rotational velocities ($v \sin i$ $\gtrsim$ 170 $\mathrm{km~s^{-1}}$) and are expected to be oblate. These interferometric measurements, the stars' observed photometric energy distributions, and $v \sin i$ values are used to computationally construct model oblate stars from which stellar properties (inclination, rotational velocity, and the radius and effective temperature as a function of latitude, etc.) are determined. The results are compared with MESA stellar evolution models (Paxton et al. 2011, 2013) to determine masses and ages. The value of this new technique is that it enables the estimation of the fundamental properties of rapidly rotating stars without the need to fully image the star. It can thus be applied to stars with sizes comparable to the interferometric resolution limit as opposed to those that are several times larger than the limit. Under the assumption of coevality, the spread in ages can be used as a test of both the prescription presented here and the MESA evolutionary code for rapidly rotating stars. With our validated technique, we combine these age estimates and determine the age of the moving group to be 414 $\pm$ 23 Myr, which is consistent with, but much more precise than previous estimates.Comment: Accepted by Ap

Re-evaluating Floor Space Allowance and Removal Strategy Effects on the Growth of Heavyweight Finishing Pigs

This study was performed to evaluate the impact of initial floor space allowance and various topping strategies (removal of the heaviest pigs in a pen prior to marketing the finishing group) on the growth performance of heavyweight finishing pigs. A total of 1,092 pigs (initially 80.1 lb) were allotted to one of 4 experimental treatments with 14 pens per treatment. The first treatment stocked pigs at 9.7 ft2 (15 pigs/pen) throughout the study. The other three treatments initially stocked pigs at 6.9 ft2. The second treatment (2:2:2) topped the two heaviest pigs on d 64 (203 lb), d 76 (227 lb), and d 95 (264 lb), which coincided with the time floor space allowance became limiting, as predicted by Gonyou et al. (2006). The third treatment (2:4) topped the 2 heaviest pigs and the 4 heaviest pigs at an average BW of 240 (d 76) and 280 lb (d 105), respectively. The fourth treatment (6) topped the 6 heaviest pigs at an average BW of 280 lb (d 105). All pigs remaining in pens after topping events were marketed on d 117 of the study. Overall (d 0 to 117), pigs in pens stocked at 9.7 ft2 had increased (P \u3c 0.05) ADG compared to pigs in pens on either the 2:4 or 6 topping strategies, but ADG was not different from pigs in pens on the 2:2:2 topping strategy. This suggests that prediction equations developed by Gonyou et al. (2006) for ADG are useful for predicting the effects of floor space on heavyweight pig ADG. Pigs in pens stocked at 9.7 ft2 had increased (P \u3c 0.05) ADFI compared to pigs in pens initially stocked at 6.9 ft2 regardless of topping strategy. Total weight gain per pen was greater (P \u3c 0.05) for pens initially stocked at 6.9 ft2 compared to pens stocked at 9.7 ft2; however, total weight gain per pig was greater for pigs in pens stocked at 9.7 ft2 compared to pigs in pens initially stocked at 6.9 ft2. Pigs in pens on the 2:2:2 topping strategy had less weight gain (P \u3c 0.05) than pigs in pens on the 6 topping strategy. Feed usage per pen was decreased for pens stocked at 9.7 ft2 compared to those initially stocked at 6.9 ft2; however, per pig feed usage was increased (P \u3c 0.05) for pigs in pens stocked at 9.7 ft2 compared to pigs in pens initially stocked at 6.9 ft2. Pens on the 2:2:2 topping strategy had less (P \u3c 0.05) feed usage, either on a pen or pig basis, than those on the 2:4 or the 6 topping strategy. Interestingly, there was a tendency (P \u3c 0.10) for pigs in pens on the 2:4 topping strategy to have less feed usage than pigs in pens on the 6 topping strategy. Income over feed and facility cost (IOFFC) was decreased (P \u3c 0.05), either on a pen or pig basis, for pens stocked at 9.7 ft2. Pigs in pens on the 2:2:2 topping strategy had numerically less IOFFC when revenue was high and feed cost was low compared to pigs in pens on the 2:4 or 6 topping strategy. In conclusion, increasing the floor space allowance or the time points at which pigs are removed from the pen improved the performance of pigs remaining in the pen; however, IOFFC may be reduced due to fewer pigs marketed from each pen (in the case of lower stocking density) or from reducing total weight produced (in pens where pigs are topped earlier at lighter weights)

Stellar Companions to Stars with Planets

A combination of high-resolution and wide-field imaging reveals two binary stars and one triple star system among the sample of the first 11 stars with planets detected by radial velocity variations. High resolution speckle or adaptive optics (AO) data probe subarcsecond scales down to the diffraction limit of the Keck 10-m or Lick 3-m, and direct images or AO images are sensitive to a wider field, extending to 10" or 38", depending upon the camera. One of the binary systems -- HD 114762 -- was not previously known to be a spatially resolved multiple system; additional data taken with the combination of Keck adaptive optics and NIRSPEC are used to characterize the new companion. The second binary system -- Tau Boo -- was a known multiple with two conflicting orbital solutions; the current data will help constrain the discrepant estimates of periastron time and separation. Another target -- 16 Cyg B -- was a known common proper motion binary, but the current data resolve a new third component, close to the wide companion 16 Cyg A. Both the HD 114762 and 16 Cyg B systems harbor planets in eccentric orbits, while the Tau Boo binary contains an extremely close planet in a tidally-circularized orbit. Although the sample is currently small, the proportion of binary systems is comparable to that measured in the field over a similar separation range. Incorporating the null result from another companion search project lowers the overall fraction of planets in binary systems, but the detections in our survey reveal that planets can form in binaries separated by less than 50 AU.Comment: 5 Tables, 16 Figures. ApJ, accepte

The Circumstellar Environments of High-Mass Protostellar Objects I: Submillimetre Continuum Emission

We present maps of the 850 micron and 450 micron continuum emission seen towards a sample of 68 high-mass protostellar candidates with luminosities ranging from 10^2.5 to 10^5 solar luminosity. Most of these candidate high-mass stars are in the earliest stages of evolution, and have not yet developed an ultra-compact HII region. We observe a variety of continuum emission morphologies, from compact symmetric sources through to multiple cores embedded in long filaments of emission. We find on average there is a 65% probability of an IRAS point-source having a companion detection at submillimetre wavelengths. The ratio of integrated flux to peak flux for our detections shows no strong dependence on distance, suggesting the emission we have observed is primarily from scale-free envelopes with power-law density structures. Assuming a near kinematic distance projection, the clumps we detect vary in mass from ~1 to over 1000 solar mass, with a mean clump mass of 330 solar mass, column density of 9x10^23 cm^-2 and diameter of ~0.6 pc. The high luminosity and low mass of the smallest clumps suggests they are accompanied by a minimal number of stellar companions, while the most massive clumps may be examples of young protogroups and protoclusters. We measure the spectral index of the dust emission (alpha) and the spectral index of the dust grain opacity (beta) towards each object, finding clumps with morphologies suggestive of strong temperature gradients, and of grain growth in their dense inner regions. We find a mean value for beta of 0.9, significantly smaller than observed towards UCHII regions.Comment: Accepted for publication in A&A (22 pages, 14 figures) Fixed missing pages in Tables 2 and

MOST detects variability on tau Bootis possibly induced by its planetary companion

(abridged) There is considerable interest in the possible interaction between parent stars and giant planetary companions in 51 Peg-type systems. We demonstrate from MOST satellite photometry and Ca II K line emission that there has been a persistent, variable region on the surface of tau Boo A which tracked its giant planetary companion for some 440 planetary revolutions and lies ~68deg (phi=0.8) in advance of the sub-planetary point. The light curves are folded on a range of periods centered on the planetary orbital period and phase dependent variability is quantified by Fourier methods and by the mean absolute deviation (MAD) of the folded data for both the photometry and the Ca II K line reversals. The region varies in brightness on the time scale of a rotation by ~1 mmag. In 2004 it resembled a dark spot of variable depth, while in 2005 it varied between bright and dark. Over the 123 planetary orbits spanned by the photometry the variable region detected in 2004 and in 2005 are synchronised to the planetary orbital period within 0.0015 d. The Ca II K line in 2001, 2002 and 2003 also shows enhanced K-line variability centered on phi=0.8, extending coverage to some 440 planetary revolutions. The apparently constant rotation period of the variable region and its rapid variation make an explanation in terms of conventional star spots unlikely. The lack of complementary variability at phi=0.3 and the detection of the variable region so far in advance of the sub-planetary point excludes tidal excitation, but the combined photometric and Ca II K line reversal results make a good case for an active region induced magnetically on the surface of tau Boo A by its planetary companion.Comment: 7 pages, 7 figures; accepted for publication in A&

Tracing the young massive high-eccentricity binary system Theta 1 Orionis C through periastron passage

The nearby high-mass star binary system Theta 1 Orionis C is the brightest and most massive of the Trapezium OB stars at the core of the Orion Nebula Cluster, and it represents a perfect laboratory to determine the fundamental parameters of young hot stars and to constrain the distance of the Orion Trapezium Cluster. Between January 2007 and March 2008, we observed T1OriC with VLTI/AMBER near-infrared (H- and K-band) long-baseline interferometry, as well as with bispectrum speckle interferometry with the ESO 3.6m and the BTA 6m telescopes (B'- and V'-band). Combining AMBER data taken with three different 3-telescope array configurations, we reconstructed the first VLTI/AMBER closure-phase aperture synthesis image, showing the T1OriC system with a resolution of approx. 2 mas. To extract the astrometric data from our spectrally dispersed AMBER data, we employed a new algorithm, which fits the wavelength-differential visibility and closure phase modulations along the H- and K-band and is insensitive to calibration errors induced, for instance, by changing atmospheric conditions. Our new astrometric measurements show that the companion has nearly completed one orbital revolution since its discovery in 1997. The derived orbital elements imply a short-period (P=11.3 yrs) and high-eccentricity orbit (e=0.6) with periastron passage around 2002.6. The new orbit is consistent with recently published radial velocity measurements, from which we can also derive the first direct constraints on the mass ratio of the binary components. We employ various methods to derive the system mass (M_system=44+/-7 M_sun) and the dynamical distance (d=410+/-20 pc), which is in remarkably good agreement with recently published trigonometric parallax measurements obtained with radio interferometry.Comment: 15 pages, 15 figures, accepted by A&

O-15 Randomized, phase 3 study of second-line tislelizumab vs chemotherapy in advanced or metastatic esophageal squamous cell carcinoma (RATIONALE 302) in the overall population and Europe/North America subgroup

Background: The global Phase 3 study RATIONALE 302 (NCT03430843) evaluated the efficacy and safety of second-line tislelizumab, an anti-PD-1 antibody, in patients with advanced or metastatic esophageal squamous cell carcinoma (ESCC). Here, we report data from the overall and Europe/North America (EU/NA) populations. Methods: Eligible adult patients had disease progression during or after first-line systemic therapy, ≥1 evaluable lesion per RECIST v1.1 and an Eastern Cooperative Oncology Group performance score (ECOG PS) of ≤1. Patients were randomized (1:1) to receive tislelizumab 200 mg intravenously Q3W or investigator-chosen chemotherapy (paclitaxel, docetaxel, or irinotecan) and treated until disease progression, intolerable toxicity, or withdrawal. Stratification factors included chemotherapy option, region, and ECOG PS. The primary endpoint was overall survival (OS) in all patients (ITT population). The key secondary endpoint was OS in PD-L1 positive (vCPS ≥10%) patients; other secondary endpoints included progression-free survival (PFS), overall response rate (ORR), duration of response (DoR), health-related quality of life and safety. Results: 512 patients (overall population) were randomized to tislelizumab (n=256) or chemotherapy (n=256), of which 108 (21%) patients were enrolled into EU/NA subgroup (n=55 tislelizumab, n=53 chemotherapy). On 1 December 2020 (data cut-off), median follow-up was 6.9 and 6.8 months in the overall population and EU/NA subgroup, respectively. Tislelizumab improved OS vs chemotherapy in the overall population (median OS 8.6 vs 6.3 months; HR 0.70, 95% CI 0.57–0.85; p=0.0001); survival benefit was consistently observed in the EU/NA subgroup (median OS 11.2 vs 6.3 months; HR 0.55; 95% CI 0.35–0.87). Treatment with tislelizumab was associated with improved ORR (20.3% [95% CI 15.6%–25.8%] vs 9.8% [95% CI 6.4%–14.1%]) and median DoR (7.1 vs 4.0 months; HR 0.42, 95% CI 0.23–0.75) vs chemotherapy in the overall population. Improvement in ORR (20.0% [95% CI 10.4%–33.0%] vs 11.3% [95% CI 4.3%–23.0%]) and median DOR (5.1 vs 2.1 months; HR 0.42, 95% CI 0.13–1.39) was also observed in the EU/NA subgroup. Fewer patients had Grade ≥3 treatment-emergent adverse events (TEAE) with tislelizumab vs chemotherapy in both the overall and EU/NA populations (46% vs 68% and 56% vs 71%, respectively). Of these, fewer Grade ≥3 AEs were treatment-related with tislelizumab vs chemotherapy (overall: 19% vs 56%; EU/NA: 13% vs 51%). AEs leading to death were similar with tislelizumab vs chemotherapy (overall: 14% vs 12%; EU/NA: 6% vs 5%). Conclusions: Second-line tislelizumab demonstrated statistically significant and clinically meaningful improvement in OS versus chemotherapy in patients with advanced or metastatic ESCC. Tislelizumab demonstrated a tolerable safety profile. Efficacy and safety results from the EU/NA subgroup were consistent with the overall population. Clinical trial identification: NCT03430843