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At least 307 records · Page 17

Soft X‐ray Spectromicroscopic Investigation of Synthetic C‐S‐H and C 3 S Hydration Products

Calcium silicate hydrates (C‐S‐H), the primary binding phase in concrete, is the most prominent physiochemical factor controlling the mechanical and chemical properties in the production of concrete. This paper reports the local‐binding structure and morphological details of C‐S‐H as determined by high‐resolution X‐ray spectromicroscopy. Hydrated tricalcium silicate (C 3 S) was used to determine the properties and role of the outer products (Op) of C 3 S. C‐S‐H with different molar ratios of Ca/Si, were synthesized (Syn‐ CSH ) to quantitatively evaluate the effect of silicate polymerization on Ca L and Si K edge of C‐S‐H. Near edge X‐ray absorption fine structure ( NEXAFS ) spectroscopy of Syn‐ CSH showed no variation in peak positions and energy separation for CaL III, II edge for the Ca/Si ratios investigated. Compared to Syn‐ CSH , C 3 S, when hydrated for 17 d, had a similar local structure around Ca. Si K edge NEXAFS analysis on Syn‐ CSH showed a tendency for the peak positions of both the Si K edge and the peak induced by multiple scattering to shift to higher energy levels. The results also indicated that the distance between the two peaks increased with a decrease of the Ca/Si ratio in Syn‐ CSH . Silicate polymerization influenced the multiple scattering of distant shell atoms more than the binding energy of the core atoms. Op of C 3 S had a uniform and higher degree of silicate polymerization compared to the core area. The results imply that Op reduces the hydration process of C 3 S into the core area thereby playing a key role on the properties of concrete upon formation.

Bae, Sungchul↗

Boundary lubrication of formulated C-ether in air to 300 deg C. 1: Phosphorus ester additives

Friction and wear measurements were made on CVM M-50 steel lubricated with three C-ether (modified polyphenyl ether) formulations in dry and wet air. Results were compared to those obtained with a formulated Type 2 ester and the C-ether base fluid. A ball-on-disk sliding friction apparatus was used. Experimental conditions were a 1-kilogram load, a 17-meter-perminute (100-rpm) surface speed, and a 25 to 300 C (77 to 572 F) disk temperature range. The C-ether base fluid and the three formulated C-ether fluids yielded lower wear than the Type 2 ester over the entire temperature range. All C-ether fluids exhibited slightly higher friction coefficients than the ester from 150 to 300 C (302 to 572 F) and similar values from 25 to 150 C (77 to 302 F). In general, lower wear rates were observed with the C-ethers when tested in wet air as compared to a dry air atmosphere.

Jones, W. R., Jr.↗

Boundary lubrication of formulated C-ethers in air to 300 C

Six C-ether formulations (containing organic acid and phosphorus ester additives) were tested in dry (less than 100 ppm H2O) and moist air (relative humidity 50 percent at 25 C) and temperatures from 25 to 300 C, in order to determine the boundary lubricating characteristics and to compare these results to those obtained with a fully formulated Type II ester and the unformulated C-ether base fluid. The apparatus, procedures and detailed results of the test are described. Friction and wear measurements were made on CVM M-50 steel under 1 kg load and 17 meter per minute (100 rpm) surface speed conditions, for a duration of 25 minutes. In general, the C-ether formulations exhibited higher friction coefficients than the ester from 150 to 300 C and similar or lower values from 25 to 150 C, furthermore, in most test conditions the C-ether base fluid and the six C-ether formulations yielded lower wear than the ester. Possible applications in the aerospace industry are mentioned.

Jones, W. R., Jr.↗

Formulation and evaluation of C-Ether fluids as lubricants useful to 260 C

Three base stocks were evaluated in bench and bearing tests to determine their suitability for use at bulk oil temperatures (BOT) from -40 C to +260 C. A polyol ester gave good bearing tests at a bulk temperature of 218 C, but only a partially successful run at 274 C. These results bracket the fluid's maximum operating temperature between these values. An extensive screening program selected lubrication additives for a C-ether (modified polyphenyl ether) base stock. One formulation lubricated a bearing for 111 hours at 274 C (BOT), but this fluid gave many deposit related problems. Other C-ether blends produced cage wear or fatigue failures. Studies of a third fluid, a C-ether/disiloxane blend, consisted of bench oxidation and lubrication tests. These showed that some additives react differently in the blend than in pure C-ethers.

Clark, F. S.↗

High-Pressure Melting Experiments of Fe 3 C and a Thermodynamic Model of Fe-C Liquids for the Earth's Core

Melting experiments of Fe 3 C were conducted to 85 GPa in laser-heated diamond anvil cells with in situ X-ray diffraction and post-experiment textural observation. From the determined pressure-temperature conditions of the melting curve for Fe 3 C, together with literature data on the melting point of diamond and eutectic point of the system Fe-Fe 3 C/Fe 7 C 3 under high pressures, we established a self-consistent thermodynamic model for high-pressure melting of the system Fe-C including the mixing parameters for liquids. The results show that mixing of Fe and C liquids is negatively nonideal from 1 bar to the pressure at the center of the Earth. The departure from ideal mixing becomes progressively larger with increasing pressure, which leads to greatly stabilized liquids under core pressures. The modeled carbon content in eutectic melts under core pressures is 3.3–4.4 wt%. From the Gibbs free energy, we derived an internally consistent parameters for Fe-C outer cores which included the crystallizing points at their bottoms, isentropic thermal profiles, and densities and longitudinal seismic wave speeds (Vp). While the addition of carbon in excess of the eutectic melt composition effectively reduces the density of iron liquid, the Vp of iron liquid is not greatly changed. Therefore, the low density and high Vp of PREM relative to pure iron cannot be reconciled by an Fe-C liquid. Therefore, the Earth's core cannot be approximated by the system Fe-C and should include another light element.

58 GEOSCIENCES↗

Observation of χ c 0 → Σ + Σ ¯ − η and evidence for χ c 1 , 2 → Σ + Σ ¯ − η

Using ( 27.12 ± 0.14 ) × 10 8 ψ ( 3686 ) events collected with the BESIII detector, the decay χ c 0 → Σ + Σ ¯ − η is observed for the first time with a signal significance of 7.0 σ , and evidence for χ c 1 → Σ + Σ ¯ − η and χ c 2 → Σ + Σ ¯ − η is found with signal significances of 4.3 σ and 4.6 σ , respectively. The branching fractions are determined to be B ( χ c 0 → Σ + Σ ¯ − η ) = ( 1.26 ± 0.20 ± 0.13 ) × 10 − 4 , B ( χ c 1 → Σ + Σ ¯ − η ) = ( 5.10 ± 1.21 ± 0.67 ) × 10 − 5 , and B ( χ c 2 → Σ + Σ ¯ − η ) = ( 5.46 ± 1.18 ± 0.50 ) × 10 − 5 , where the first uncertainties are statistical, and the second ones are systematic. Published by the American Physical Society 2024

Ablikim, M.↗

Search for e + e − → φ χ c 0 and φ η c 2 ( 1 D ) at center-of-mass energies from 4.47 to 4.95 GeV

Utilizing a dataset of 6.7 fb − 1 from electron-positron collisions recorded by the BESIII detector at the BEPCII storage ring, a search is conducted for the processes e + e − → ϕ χ c 0 and ϕ η c 2 ( 1 D ) across center-of-mass energies from 4.47 to 4.95 GeV. In the absence of any significant signals, upper limits are set. These include limits on the dressed cross sections for e + e − → ϕ χ c 0 , as well as the product of the dressed cross section for e + e − → ϕ η c 2 ( 1 D ) and a sum of five branching fractions. Furthermore, the product of the electronic width of Y ( 4660 ) and the branching fraction of the Y ( 4660 ) → ϕ χ c 0 , denoted as Γ e + e − Y ( 4660 ) B Y ( 4660 ) → ϕ χ c 0 , is determined to be < 0.35 eV at the 90% confidence level. Published by the American Physical Society 2025

Ablikim, M.↗

Observation of New Ω c 0 States Decaying to the Ξ c + K - Final State

Two new excited states, Ω c (3185) 0 and Ω c ⁢(3327) 0 , are observed in the $Ξ^{+}_{c}$K - invariant-mass spectrum using proton-proton collision data collected by the LHCb experiment, corresponding to an integrated luminosity of 9 fb -1 . Five previously observed excited $Ω^{0}_{c}$ states are confirmed, namely Ω c ⁢(3000) 0 , Ω c ⁢(3050) 0 , Ω c⁢ (3065) 0 , Ω c⁢ (3090) 0 , and Ω c⁢ (3119) 0 . The masses and widths of these seven states are measured with the highest precision to date.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Investigating {sup 13}C+{sup 12}C reaction by the activation method. Sensitivity tests

We have performed experiments to check the limits of sensitivity of the activation method using the new 3 MV Tandetron accelerator and the low and ultra-low background laboratories of the “Horia Hulubei” National Institute of Physics and Nuclear Engineering (IFIN-HH). We have used the {sup 12}C+{sup 13}C reaction at beam energies E{sub lab}= 6, 7 and 8 MeV. The knowledge of this fusion cross section at deep sub-barrier energies is of interest for astrophysical applications, as it provides an upper limit for the fusion cross section of {sup 12}C+{sup 12}C over a wide energy range. A {sup 13}C beam with intensities 0.5–2 particleμA was provided by the accelerator and used to bombard graphite targets, resulting in activation with {sup 24}Na from the {sup 12}C({sup 13}C,p) reaction. The 1369 and 2754 keV gamma-rays from {sup 24}Na de-activation were clearly observed in the spectra obtained in two different laboratories used for measurements at low and ultralow background: one at the surface and one located underground in the Unirea salt mine from Slanic Prahova, Romania. In the underground laboratory, for E{sub lab} = 6 MeV we have measured an activity of 0.085 ± 0.011 Bq, corresponding to cross sections of 1–3 nb. This demonstrates that it is possible to measure {sup 12}C targets irradiated at lower energies for at least 10 times lower cross sections than before β–γ coincidences will lead us another factor of 10 lower, proving that this installations can be successfully used for nuclear astrophysics measurements.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

On the Linearity of Local and Regional Temperature Changes from 1.5°C to 2°C of Global Warming

Because of the Paris Agreement it is imperative there is greater understanding of the consequences of limiting global warming to the target 1.5° and 2°C levels above preindustrial conditions. It is challenging to quantify changes across a small increment of global warming, so a pattern-scaling approach may be considered. Here we investigate the validity of such an approach by comprehensively examining how well local temperatures and warming trends in a 1.5°C world predict local temperatures at global warming of 2°C. Ensembles of transient coupled climate simulations from multiple models under different scenarios were compared and individual model responses were analyzed. For many places, the multimodel forced response of seasonal-average temperatures is approximately linear with global warming between 1.5° and 2°C. Yet, individual model results vary and large contributions from nonlinear changes in unforced variability or the forced response cannot be ruled out. In some regions, such as East Asia, models simulate substantially greater warming than is expected from linear scaling. Examining East Asia during boreal summer, we find that increased warming in the simulated 2°C world relative to scaling up from 1.5°C is related to reduced anthropogenic aerosol emissions. Our results indicate that, where forcings other than those due to greenhouse gas emissions change, the warming experienced in a 1.5°C world is a poor predictor for local climate at 2°C of global warming. In addition to the analysis of the linearity in the forced climate change signal, we find that natural variability remains a substantial contribution to uncertainty at these low-warming targets.

54 ENVIRONMENTAL SCIENCES↗

Coordinating AgMIP Data and Models Across Global and Regional Scales for 1.5°C and 2.0°C Assessments

The Agricultural Model Intercomparison and Improvement Project (AgMIP) has developed novel methods for Coordinated Global and Regional Assessments (CGRA) of agriculture and food security in a changing world. The present study aims to perform a proof of concept of the CGRA to demonstrate advantages and challenges of the proposed framework. This effort responds to the request by the UN Framework Convention on Climate Change (UNFCCC) for the implications of limiting global temperature increases to 1.5°C and 2.0°C above pre-industrial conditions. The protocols for the 1.5°C/2.0°C assessment establish explicit and testable linkages across disciplines and scales, connecting outputs and inputs from the Shared Socio-economic Pathways (SSPs), Representative Agricultural Pathways (RAPs), Half a degree Additional warming, Prognosis and Projected Impacts (HAPPI) and Coupled Model Intercomparison Project Phase 5 (CMIP5) ensemble scenarios, global gridded crop models, global agricultural economics models, site-based crop models and within-country regional economics models. The CGRA consistently links disciplines, models and scales in order to track the complex chain of climate impacts and identify key vulnerabilities, feedbacks and uncertainties in managing future risk. CGRA proof-of-concept results show that, at the global scale, there are mixed areas of positive and negative simulated wheat and maize yield changes, with declines in some bread basket regions, at both 1.5°C and 2.0°C. Declines are especially evident in simulations that do not take into account direct CO2 effects on crops. These projected global yield changes mostly resulted in increases in prices and areas of wheat and maize in two global economics models. Regional simulations for 1.5°C and 2.0°C using site-based crop models had mixed results depending on the region and the crop. In conjunction with price changes from the global economics models, productivity declines in the Punjab, Pakistan, resulted in an increase in vulnerable households and the poverty rate. This article is part of the theme issue ‘The Paris Agreement: understanding the physical and social challenges for a warming world of 1.5°C above pre-industrial levels’.

interdisciplinary↗

A DFT Comparison of C–C Reductive Coupling from Terminal Cyanido and Cyaphido Complexes of Nickel

The density functional theory study of the thermal C–C reductive coupling from terminal cyanido and hypothetical cyaphido complexes of [Ni(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) revealed the key reaction intermediate in the reductive C–CP coupling being a σ-CC complex unlike an η 2 -aryl complex in the Ni C–CN system, as already observed in our previous studies. The reaction in THF is endothermic by 4.9 kcal/mol for cyanido with a 32.0 kcal/mol activation barrier and exothermic by 28.5 kcal/mol for cyaphido with an 11.3 kcal/mol activation barrier. To compare our results with the existing experimental data, we chose mesityl as the aryl group and also studied the CP reaction with [Pt(dmpe)] and [Pt(dmpm)] (dmpe = 1,2-bis(dimethylphosphino)methane) fragments. Our findings are consistent with the thermodynamically uphill photolytic C–CP bond activation in phosphaalkynes with Pt and a faster thermal back-reaction with [Pt(dmpe)] compared to that of [Pt(dmpm)]. Furthermore, based on the natural population analysis, when the polarity of the C–C bond is inverted, the sign of ΔG° is also inverted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Search for new hadronic decays of $h_c$ and observation of $h_c$ → $p\overline{p}η$

A search for the hadronic decays of the $h_c$ meson to the final states $p\overline{p}π^+π^-π^o$, $p\overline{p}η$, and $p\overline{p}π^o$ via the process $\psi$(3686) → $π^oh_c$ is performed using (4.48 ± 0.03) x 10 8 $\psi$(3686) events collected with the BESIII detector. The decay channel $h_c$ → $p\overline{p}η$ is observed for the first time with a significance greater than 5σ and a branching fraction of (6.41 ± 1.74 ± 0.53 ± 1.00) x 10 -4 , where the uncertainties are statistical, systematic, and that from the branching fraction of $\psi$(3686) → $π^oh_c$. Strong evidence for the decay $h_c$ → $p\overline{p}π^+π^-π^o$ is found with a significance of 4.9σ and a branching fraction of (3.84 ± 0.83 ± 0.69 ± 0.58) x 10 -3 . The significances include systematic uncertainties. No clear signal of the decay $h_c$ → $p\overline{p}π^o$ is found, and an upper limit of 6.59 x 10 -4 on its branching fraction is set at the 90% confidence level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Observation of Structures in the Processes e + e − → ω χ c 1 and ω χ c 2

We present measurements of the Born cross sections for the processes e + e − → ω χ c 1 and ω χ c 2 at center-of-mass energies s from 4.308 to 4.951 GeV. The measurements are performed with data samples corresponding to an integrated luminosity of 11.0 fb − 1 collected with the BESIII detector operating at the Beijing Electron Positron Collider storage ring. Assuming the e + e − → ω χ c 2 signals come from a single resonance, the mass and width are determined to be M = ( 4413.6 ± 9.0 ± 0.8 ) MeV / c 2 and Γ = ( 110.5 ± 15.0 ± 2.9 ) MeV , respectively, which is consistent with the parameters of the well-established resonance ψ ( 4415 ) . In addition, we also use one single resonance to describe the e + e − → ω χ c 1 line shape and determine the mass and width to be M = ( 4544.2 ± 18.7 ± 1.7 ) MeV / c 2 and Γ = ( 116.1 ± 33.5 ± 1.7 ) MeV , respectively. The structure of this line shape, observed for the first time, requires further understanding. Published by the American Physical Society 2024

Physics↗

Copper‐Catalyzed C(sp 3 )−H Amidation: Sterically Driven Primary and Secondary C−H Site‐Selectivity

Abstract Undirected C(sp 3 )−H functionalization reactions often follow site‐selectivity patterns that mirror the corresponding C−H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C−H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C−H bonds over tertiary and benzylic C−H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C−H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N 3 . Mechanistic and DFT studies indicate that C−H amidation involves H‐atom abstraction from R‐H substrates by nitrene intermediates [Cu](κ 2 ‐ N , O ‐NC(O)Ar) to provide carbon‐based radicals R . and copper(II)amide intermediates [Cu II ]‐NHC(O)Ar that subsequently capture radicals R . to form products R‐NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C−H amidation selectivity in the absence of directing groups.

Bakhoda, Abolghasem (Gus)↗

Comparison of the Phase Stability and Corrosion Resistance of the Ni-Based Alloys C-4 and C-276

A one-to-one correspondence is developed between the phase stability and corrosion resistance of the commercial (Ni-Cr-Mo)-based alloys C-276 and C-4. Alloy C-4 is shown to outperform alloy C-276 in acidic oxidizing media and approaches its resistance in acidic reducing media. Both alloys are found to have similar resistance to chloride-induced stress corrosion cracking in the annealed condition with short-range order. The aqueous corrosion resistance of both alloys is found to be improved by long-range order; however, they become highly susceptible to chloride-induced stress corrosion cracking. Alloy C-4 is distinguished by being stable toward precipitation of detrimental intermetallic compounds. However, alloy C-276 is shown to be prone to precipitation of mu phase which degrades its resistance to aqueous corrosion and chloride-induced stress corrosion cracking. It is concluded that the chemical composition of alloy C-4 is tailored to make it more versatile than alloy C-276 in acidic oxidizing media and the results are found to be consistent with the concept of atomic percent factor of each alloy.

36 MATERIALS SCIENCE↗

Hydrogenation and C-S bond activation pathways in thiophene and tetrahydrothiophene reactions on sulfur-passivated surfaces of Ru, Pt, and Re nanoparticles

Thiophene-H2 reactions proceed via sulfur removal and hydrogenation routes on dispersed metal nanoparticles that become decorated by refractory S-adlayers during catalysis. The identity and kinetic relevance of the required elementary steps are described here based on rates measured at S-chemical potentials set by H2S/H2 ratios similar to those prevalent during practical catalysis on Re, ReSx, Ru, and Pt catalysts. Free energies for S adatom formation (from H2S decomposition and H2 evolution) are strongly exothermic (< -50 kJ mol-1 on Pt(111) and < -150 kJ mol-1 on Re and Ru(0001)), but strong repulsions between S adatoms cause adsorption free energies to increase significantly with coverage on all three surfaces, preventing complete monolayer formation. These adlayers, composed of unreactive S-atoms (S') that cover 1/3–2/3 ML leave residual interstitial spaces (*) that bind S-atoms (S*), intermediates, and transition states reversibly, as required for catalytic turnovers. The number and binding properties of these interstices depend on the identity and chemical state of the nanoparticle bulk phase, which influences S'-binding and coverages and cause large differences in direct desulfurization and hydrogenation turnover rates (per exposed metal atom) on dispersed Re, ReSx, Ru, and Pt. The identity and kinetic relevance of elementary steps for desulfurization (to C4¬ hydrocarbons) and hydrogenation (to tetrahydrothiophene; THT) are similar among these catalysts; they involve the kinetically-relevant formation of a thiophene-derived intermediate (monohydrothiophene on Re and ReSx; dihydrothiophene on Ru and Pt) that either cleaves its C-S bond or “over-hydrogenates” to THT in one surface sojourn. THT then undergoes C-S bond cleavage in secondary reactions that correct such over-hydrogenation to form the more unsaturated species that cleave C-S bonds. THT/C4 product ratios are insensitive to H2S/H2 ratios and thiophene pressure, even though active interstitial spaces are covered by kinetically-detectable coverages of S* and thiophene; therefore, primary and secondary reactions must involve the same active surfaces. The observed increase in THT/C4 ratios with H2 pressure shows that THT formation transition states involve a larger number of H-atoms than for C-S cleavage. The requirement for bound species with intermediate unsaturation (between THT and thiophene) for C-S bond cleavage is reminiscent of the H-shuttling required in C-C and C-O hydrogenolysis, reactions that involve the partial dehydrogenation of alkanes and alkanols, respectively, to weaken such bonds and to increase the formation entropy of the relevant transition states via the evolution of H2(g). These mechanistic details challenge prevalent paradigms about different site requirements for hydrogenation and desulfurization pathways and about how metal-sulfur bond energies act as descriptors of reactivity; in fact, such binding energies merely act to define the refractory S-adlayers that enable the formation of weakly-binding interstices that reversibly bind intermediates and transition states, thus allowing catalytic turnovers.

Yik, Edwin↗