Dehydrogenation of Light Alkanes Over Rhenium Catalysts on Conventional and Mesoporous MFI Supports

Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time on stream due to deactivation of the catalyst. We show that by use of rhenium impregnated MFI supports with very few or no acidic sites (Si/Al > 500), highly selective ethane dehydrogenation catalysts are obtained with ethene selectivities of 98%. By use of mesoporous MFI supports (Si/Al >500) the lifetime of the catalyst appears to be slightly improved compared to conventional MFI crystals. The beneficial effect of a mesoporous MFI support is convincingly demonstrated in propane dehydrogenation, where both conversion and selectivities on the mesoporous MFI (Si/Al > 500) impregnated with Re are significantly higher than on Re supported on a comparable conventional MFI support.     

Mullite Coatings on SiC and C/C–Si–SiC Substrates Characterized by Infrared Spectroscopy

Mullite (3Al₂O₃·2SiO₂) coatings on SiC substrates and SiC precoated carbon/carbon composite (C/C-Si-SiC) substrates were produced by pulsed laser deposition (PLD) using pressed mullite powder targets. The layers can be characterized efficiently by IR reflection spectroscopy in the spectral range between 650 and 5000 cm⁻¹. The deposited coatings turn into mullite upon oxidation in air at temperatures between 1400° and 1600°C. Fabry-Perot interferences indicate a high quality and homogeneity of the mullite coating/SiC substrate interface. Amorphous SiO₂ gradually forms during prolonged heating or at higher temperatures.     

Integration Concepts for the Fabrication of LTCC Structures

At the Keck Smart Materials Integration Laboratory at Penn State University, low-temperature co-fired ceramic (LTCC) material systems have been used to fabricate a number of devices for a variety of applications. This article presents an overview of the integration of the concepts and materials that we have used to achieve miniaturization and unique device function. Examples of microwave filters, metamaterial antennas, and a dielectrophoretic cell sorter will be presented, with emphasis on device modeling and design, prototype construction methods, and test results.     

Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

Characterisation and tribological evaluation of nitrogen-containing molybdenum–copper PVD metallic nanocomposite films

This paper reports on the structural, mechanical and tribological properties of molybdenum–copper nanocomposite films ‘doped’ with small amounts of nitrogen, which contain either no nitride phase (i.e. the nitrogen is held in interstitial solid solution, mainly in molybdenum) or small amounts of lower nitrides (i.e. Mo₂N). All films were deposited on Si wafers, AISI M2 high speed steel and AISI 316 stainless steel by reactive sputtering using a hot-filament-enhanced dc unbalanced magnetron system. A systematic approach was adopted to investigate the evolution of metal/metal and ceramic/metal phase combinations with increasing nitrogen content (up to 40 at.% N) in the film. Coating composition and microstructure were determined by cross-sectional TEM, SEM and XPS. XRD was used to identify (where possible) metallic and metal-nitride phases. Mechanical properties such as hardness and elastic modulus were determined by low load Knoop and instrumented Vickers indentation measurements. Reciprocating sliding, micro-abrasion and impact tests were performed to assess tribological performance.

It was found that increasing the nitrogen gas flow rate from 0 to 15 sccm (and therefore nitrogen content in the film from 0 to 24 at.% N), refined significantly the coating microstructure from columnar to a dense and more equiaxed morphology, increasing the hardness whilst maintaining (almost constant) elastic modulus values, close to that of molybdenum metal. Further increases in the nitrogen gas flow rate resulted in films that appeared to contain significant fractions of the Mo₂N ceramic phase. SEM and cross-sectional TEM analyses of the film deposited at a nitrogen flow rate of 20 sccm (containing 36 at.% N) demonstrated a microstructure consisting of 50–100 nm wide columns, which contain small regions of contrast in dark-field images, of the order of 3–5 nm wide. A maximum hardness of 32 GPa and the highest hardness/modulus ratio was however found in the (predominantly metallic) film deposited at a nitrogen gas flow rate of 15 sccm. This film also performed best in both micro-abrasion and impact wear tests; in contrast, the ‘ceramic’ film (deposited at 20 sccm nitrogen flow rate) performed better in reciprocating sliding wear.     

High pressure cell for neutron reflectivity measurements up to 2500 bar

The design of a high pressure (HP) cell for neutron reflectivity experiments is described. The cell can be used to study solid-liquid interfaces under pressures up to 2500 bar (250 MPa). The sample interface is based on a thick silicon block with an area of about 14 cm(2). This area is in contact with the sample solution which has a volume of only 6 cm(3). The sample solution is separated from the pressure transmitting medium, water, by a thin flexible polymer membrane. In addition, the HP cell can be temperature-controlled by a water bath in the range 5-75°C. By using an aluminum alloy as window material, the assembled HP cell provides a neutron transmission as high as 41%. The maximum angle of incidence that can be used in reflectivity experiments is 7.5°. The large accessible pressure range and the low required volume of the sample solution make this HP cell highly suitable for studying pressure-induced structural changes of interfacial proteins, supported lipid membranes, and, in general, biomolecular systems that are available in small quantities, only. To illustrate the performance of the HP cell, we present neutron reflectivity data of a protein adsorbate under high pressure and a lipid film which undergoes several phase transitions upon pressurization.     

Physiological aspects of androstenone and skatole formation in the boar-A review with experimental data

The advantages of boars in fattening performance and carcass traits when compared with the other sexes are explained by testicular anabolic hormones. The steroid androstenone with a pronounced urine-like odour is the main objection against boar meat. More recently skatole (faecal odour) has been identified as another contributor to off-odour of pork. Androstenone is synthesized in the testes, secreted into the circulation and accumulated in adipose tissue due to its lipophilic property. Its biosynthesis is linked to the synthesis of anabolic testicular hormones. Therefore no practical method is available to maintain the sex-dependent anabolic potential of boars and to suppress androstenone selectively. Skatole is formed from tryptophan by specialized microbes in the colon when energy in the colon is limited. Gonadal hormones, but also growth hormone and IGF-1, favour its formation. Oestrogens, which are synthesized in high amounts in boar testes, decrease voluntary food intake, thus lowering the intestinal passage rate. Additionally oestrogens probably influence directly intestinal contractions via specific gut receptors. It appears, however, that glucocorticoids are more important. They counteract mitogenic hormones, such as IGF-1, ultimately leading to gut mucosal cell degradation. The resulting cell debris probably is the main source of tryptophan for microbial skatole formation. In contrast to androstenone, skatole formation can be easily suppressed by dietary means.     

Effect of external index of refraction on multimode fiber couplers

The dependence of the performance of fused-taper multimode fiber couplers on the refractive index of the material surrounding the taper region has been investigated both theoretically and experimentally. It has been identified that for a 2 × 2 multimode fiber coupler there is a range of output-power-coupling ratios for which the effect of the external refractive index is negligible. When the coupler is tapered beyond this region, the performance becomes dependent on the external index of refraction and lossy. To analyze the multimode coupler-loss mechanism, we develop a two-dimensional ray-optics model that incorporates trapped cladding-mode loss and core-mode loss through frustrated total internal reflection.

Computer-simulation results support the experimental observations. Related issues such as coupler fabrication and packaging are also discussed.

     

Photocatalytic Valorization of Plastic Waste over Zinc Oxide Encapsulated in a Metal–Organic Framework

The conversion of waste plastic into high-value-added chemicals is regarded as a promising approach for relieving global plastic pollution and contributing to the circular economy. Herein, a partial calcination strategy is developed to fabricate a zinc oxide/UiO66-NH₂ (ZnO/UiO66-NH₂) heterojunction, in which ZnO is encapsulated in porous UiO66-NH₂ for the photocatalytic valorization of plastic. This strategy preserves the framework structure of UiO66-NH₂, thus enabling the formation of ZnO with ultra-small size distributed inside the skeleton. The synergistic effect of the obtained ZnO/UiO66-NH₂ heterojunction facilitates providing an efficient channel for carrier/mass transfer and guarantees structural stability. As a result, ZnO/UiO66-NH₂ exhibits high activity for converting polylactic acid (PLA) and polyvinyl chloride (PVC) into acetic acid, coupled with H₂ production. This work provides a feasible strategy for rationally designing heterojunction photocatalysts, as well as an insight into understanding the process of photocatalytic valorization of plastic.     

Long‐term effects of angiotensin II blockade with irbesartan on inflammatory markers in hemodialysis patients: A randomized double blind placebo controlled trial (SAFIR study)

Introduction: Low‐grade chronic inflammation is common in hemodialysis (HD) patients. Previous studies suggest an anti‐inflammatory effect of angiotensin II receptor blocker (ARB) treatment. The aim of this study was to compare the effect of ARB vs. placebo on plasma concentrations of inflammatory markers in HD patients. Methods: Adult HD patients were randomized for double‐blind treatment with the ARB irbesartan 150–300 mg/day or placebo. At baseline, 1 week, 3, 6, 9, and 12 months plasma high sensitivity C‐reactive protein (hsCRP), interleukin (IL)?1β, IL‐6, IL‐8, IL‐18, and transforming growth factor‐β (TGF‐β) were measured using Luminex and enzyme‐linked immunosorbent assay (ELISA) technology. Findings: Eighty‐two patients were randomized (placebo/ARB: 41/41). The groups did not differ in initial levels of any of the inflammatory markers (placebo/ARB median(range)): hsCRP 3.3(0.2–23.4)/2.7(0.2–29.6) μg/mL; IL‐1β 1.1(0.0–45.9)/1.1(0.0‐7.2) pg/mL; IL‐6 10(1–90)/12(1–84) pg/mL; IL‐8 31(9–134)/34(5–192) pg/mL; IL‐18 364(188–1343)/377(213–832) pg/mL; TGF‐β 3.2(0.8–13.9)/3.6(1.3–3.8) ng/mL. Overall, there was no significant difference in hsCRP, IL‐6, IL‐8, and TGF‐β between placebo and ARB‐treated patients during the study period, and hsCRP, IL‐6, IL‐8, and TGF‐β were relatively stable during the study period (P ≥ 0.18 in all tests for parallel curves, equal levels, and constant levels). The IL‐1β level was slightly different in the two groups over time, but not significantly (P = 0.09 in test for parallel curves) and it was also relatively stable during the study period (P ≥ 0.49 in tests for equal levels and constant level). IL‐18 was the only inflammatory marker which was not constant during the study period (P = 0.001 in test for constant level), but there was no significant difference between placebo and ARB‐treated (P ≥ 0.51 in tests for parallel curves and equal levels). Discussion: Inflammatory biomarkers were neither acutely, nor in the long‐term significantly affected by the ARB irbesartan. Our findings suggest that ARB treatment in HD patients does not offer protective anti‐inflammatory effects.