Free CH Research Articles

Experimental analysis on light weight concrete utilizing compost and Ground Granulated Blast Furnace Slag (GGBS): Insights into elevated temperature properties through TGA

AbstractWhenever a new material is replaced in concrete, some other tests other than strength and durability need to be carried out to validate the viability of the material replaced. This study aims to investigate the sustaining capacity of the light weight concrete manufactured with compost and Ground Granulated Blast Furnace Slag (GGBS) for M sand and cement respectively subjected to high temperature. Four concrete samples are tested, which includes the control specimen and three specimens are opted based on the optimum mix arrived from the strength and durability studies. Thermogravimetric Analysis (TGA) is done on the samples and they are heated up to 1,000 °C. For the specimens tested, the loss in mass with respect to the temperature is obtained. It is noted that the mass loss of the concrete samples with 15% GGBS along with compost at 0 & 10% is found lower than the control specimen. Also, from the loss in mass, the loss of chemically bound water and free CH content can be found, which aids in contributing strength to the concrete. For the concrete to be sustainable, compost can be replaced at 10% and GGBS at 15%.

Modular synthesis of unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene molecular semiconductors for organic transistors.

A modular approach to underexplored, unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene (BTBT) scaffolds delivers a library of BTBT materials from readily available coupling partners by combining a transition-metal free Pummerer CH–CH-type cross-coupling and a Newman–Kwart reaction. This effective approach to unsymmetrical BTBT materials has allowed their properties to be studied. In particular, tuning the functional groups on the BTBT scaffold allows the solid-state assembly and molecular orbital energy levels to be modulated. Investigation of the charge transport properties of BTBT-containing small-molecule:polymer blends revealed the importance of molecular ordering during phase segregation and matching the highest occupied molecular orbital energy level with that of the semiconducting polymer binder, polyindacenodithiophene-benzothiadiazole (PIDTBT). The hole mobilities extracted from transistors fabricated using blends of PIDTBT with phenyl or methoxy functionalized unsymmetrical BTBTs were double those measured for devices fabricated using pristine PIDTBT. This study underscores the value of the synthetic methodology in providing a platform from which to study structure–property relationships in an underrepresented family of unsymmetrical BTBT molecular semiconductors.

Heterogeneous Transport of Free CH4 and Free CO2 in Dual-Porosity Media Controlled by Anisotropic In Situ Stress during Shale Gas Production by CO2 Flooding: Implications for CO2 Geological Storage and Utilization.

Regarding shale gas production by CO2 flooding, few existing reports explain the performance of free CH4 and free CO2 in shale reservoirs controlled by anisotropic in situ stress, partly restricting the integrated recognition of shale-based CO2 geological storage and utilization (CGSU). In this work, a self-developed model embedded with thermo-hydro-mechanical coupling relationships is introduced to investigate how the anisotropic in situ stress determines the transport of free gases (CH4 and CO2) after CO2 is injected into the shale. Therefore, the stronger anisotropy of in situ stress enables more CO2 in the free phase to be trapped in the shale reservoir and is insignificant for the content of residual free CH4 compared to the situation under isotropic in situ stress. Along with CO2 injection into the shale, the matrix porosity decreases invariably, while the fracture porosity decreases first and then increases gradually. Therein, the variation amplitude of the matrix/fracture porosity is more distinct under a stronger anisotropic in situ stress. The simulations also suggest that the ratio of free CO2 relative to all free gases in shale is ∼65% at most after sufficient CGSU operation. Hopefully, this comprehensive work is helpful in enhancing the knowledge on the promising shale-based low-carbon CGSU technique.

Anisotropic Permeability Influencing the Performance of Free CH4 and Free CO2 during the Process of CO2 Sequestration and Enhanced Gas Recovery (CS-EGR) from Shale

To explore how anisotropic permeability affects the performance of free gases (CO2 and CH4) during the process of sequestrate CO2 and enhance gas recovery (CS-EGR) in shale reservoirs, this work de...

Effects of High-Fat Diet on Steatosis, Endoplasmic Reticulum Stress and Autophagy in Liver of Tilapia (Oreochromis niloticus)

Hepatic steatosis is the most common phenomenon of lipid metabolism disorder in farmed fish, but its molecular mechanism is poorly understood. Therefore, the present study was aimed to investigate steatosis induced by high-fat diet (HFD) and explore underlying mechanism in tilapia. The fish were fed on control diet or HFD for 90 days. The blood and liver tissues were collected to determine biochemical parameters, genes expression and proteins level after 30, 60 and 90 days and analyzed lipid accumulation, endoplasmic reticulum (ER) stress and autophagy. After 30 days of feeding, the plasma and hepatic lipid content (TG, TCH, LDL-C and HDL-C) and fatty acids (FAs) transportation (fabp1 and CD36) were enhanced significantly in HFD-fed tilapia. After 60 days, the lipid metabolism disorder, such as increase of TG synthesis and free CH formation, and decrease of FAs β-oxidation and biosynthesis, was observed in liver of HFD-fed tilapia. Further, with increasing lipid accumulation, ER stress was induced and worsen hepatic steatosis via activating IRE1 signaling pathway in liver of HFD group after 90 days. Meanwhile, the autophagy was suppressed via impairing AMPK and BFET pathways in HFD-fed tilapia liver after 90 days. Our results demonstrated that HFD feeding induced extensive lipid deposition, promoted ER stress, suppressed autophagy in tilapia liver. Interestingly, these pathological features were positively correlated with the duration of HFD feeding.

Insights into deactivation mechanism of sulfonated carbonaceous solid acids probed by cellulose hydrolysis

Sulfonated carbonaceous solid acids are key heterogeneous catalysts and are widely used in acid-catalyzed reactions, especially in biomass transformation. In this work, the sulfonated carbonaceous solid acids were prepared and their stability was examined in cellulose hydrolysis at 170 °C. Their activity decreased largely after the hydrothermal treatment at 170 °C, as a result of the leaching of their SO3H species. Characterizations of the filtrates after the hydrothermal treatment of these solid acid catalysts by NMR and laser scattering demonstrated that the leaching of SO3H sites was not caused by the cleavage of CS bonds, but by the exfoliation of colloidal carbon particles with SO3H sites from the catalysts. Such leaching problem led to significant decrease in SO3H density for the carbon-based solid acids that synthesized by traditional sulfonation methods because of their uneven distribution of SO3H sites. To address this issue, carbon precursors with more free CH sites were applied to regulate the distribution of SO3H sites. As a consequence, the evenly distributed SO3H sites resulted in less change in acid density after the hydrothermal treatment, and maintenance of high SO3H density. This study could provide new guidance to further design of water-tolerant solid acid catalysts, and would promote the development of energetically efficient processes to convert cellulose.

Design and Simulation of High Efficiency Tin Halide Perovskite Solar Cell

Perovskite solar cells are becoming dominant alternative for the traditional solar cells reaching an efficiency of 22.1% in a short span of eight years (2008-2016). In this work we designed a tin based perovskite simulated model with novel architecture of Glass/ZnO:Al/TiO 2 /CH 3 NH 3 SnI 3 /CuI/Au and analysed using the solar cell capacitance simulator (SCAPS-1D), which is well adapted to study the photovoltaic architectures. Using this software tool, we studied the effect of absorber layer parameters on the photovoltaic parameters of the designed model. We optimized the thickness, defect density, band gap of absorber layer and operating temperature of the model by simulating at various conditions. With the optimized thickness (0.6 µm), defect density of absorber layer (10 14 cm -3 ), band gap(1.3 eV) the encouraging result of maximum power conversion efficiency(PCE) 24.82%, the short circuit current density(Jsc) is 25.67 mA/cm 2 , and fill factor(FF) is78.14% and open circuit voltage(Voc) is 1.0413V are predicted. The results are indicating that the lead free CH 3 NH 3 SnI 3 is having the great potential to be an absorber layer with suitable in organic hole transport material like CuI to achieve high efficiency. This simulation model will become a good guide for the fabrication of high efficiency tin based perovskite solar cell.

Effects of Molecular Weight below the Entanglement Threshold on Interfacial Nanoparticles/Polymer Dynamics

This work deals with effects of polymer molecular weight, Wm, below the entanglement threshold, Wm,e, on molecular dynamics of polydimethylsiloxane (PDMS) adsorbed onto silica particles, employing differential scanning calorimetry (DSC) and two dielectric techniques: broadband dielectric spectroscopy (BDS) and thermally stimulated depolarization currents (TSDC). The rigid amorphous polymer fraction at interfaces, RAFint, was found suppressed for larger Wm by all techniques in qualitative agreement with each other. Results on RAFint were supported by evaluating, for the first time, the coverage of hydroxyls at the surfaces of nanoparticles by polymer chains (S relaxation). The mobility of interfacial polymer (αint relaxation) was followed by BDS and TSDC, showing suppression of dynamics and cooperativity with decreasing Wm. We suggest that interfacial polymer fraction and dynamics are dominated by the concentration of polymer–particle contact points, the latter increasing for smaller Wm due to more free ch...

Comparative study of the characteristics of nano silica - , silica fume - and fly ash - incorporated cement mortars

The structural characteristics of cement mortars, impregnated with nano silica (NS), silica fume (SF) and fly ash (FA), were comparatively studied using Fourier transform infrared spectrometer (FTIR), thermogravimeter-differential thermogravimeter (TG-DTG) and scanning electron microscope (SEM). The mechanical strengths of the specimens were determined at early (7th day) and standard (28th day) curing ages. The compressive strengths and flexural strengths developed in the mortar specimens containing NS particles were found considerably higher than those of the corresponding specimens of SF and FA over and above the control at both ages. FTIR, TG-DTG and SEM analyses results were consistent with the remarkable increase in the mechanical strength of the mortars with NS. These increases in the strengths of the mortars with NS are attributable to the nano sized particles and extensive surface area of NS. The nano sized particles, as nucleating agents, promoted the hydration of C3S and C2S and the formation of C - S - H phase. Plenty of active sites on the surface of NS particles induced their pozzolanic reactivity and the extent of bond formation between NS particles and free CH.

Physicochemical factors impacting CO2 sequestration in depleted shale formations: The case of the Utica shale

Abstract Fractured shale formations could serve as an attractive target formation for geologic carbon sequestration once they have been depleted of hydrocarbons. The low intrinsic permeability of the shale matrix could reduce the CO 2 leakage potential, the kerogen in the shale would provide a matrix within which the CO 2 can be permanently sorbed, and the infrastructure in place at gas production sites could all be leveraged to minimize costs. Here, a modeling framework previously developed by the authors to estimate the sequestration capacity of shale formations is extended to better capture the physicochemical realities associated with injecting CO 2 into fractured shale formations. The model uses CH 4 production data to fit key parameters about the formation and applies those to a unipore diffusion model to characterize the controlling gas transport processes. A number of parameters, including the gas diffusion coefficient, the ratio of adsorbed gas to free phase gas, water saturation and gas adsorption isotherms are considered and their effect on modeling estimates is explored. The model is found to be most sensitive to the ratio of adsorbed gas to the total gas which includes both adsorbed and free phase gas. The equilibrium adsorption parameters of CH 4 and CO 2 also have significant influence largely because published estimates for these parameters vary considerably. The effect of pore collapse following production was explored in terms of its effect on characteristic diffusion length. The results indicate that increasing this characteristics length by an order of five would triple the time it takes to complete the injection of CO 2 into the formation. Similarly, an increase in water content in the formation or in the ratio of free CH 4 to sorbed CH 4 would decrease the sequestration potential of the formation. Based on this improved constitutive understanding of the modeling inputs and the estimates, the CO 2 sequestration capacity of the Utica Shale was calculated and the results were compared with those from Marcellus Shale. The differences could be understood in terms of the distinct petrophysical properties of those two shale formations. This analysis provides recommendations about experimental directions that could be very useful for improving the accuracy of sequestration capacity models.

Sensing combustion intermediates by femtosecond filament excitation

Simultaneous monitoring of multiple combustion intermediates using femtosecond filament-induced nonlinear spectroscopy is demonstrated. Clean fluorescence emissions from free radicals CH, CN, NH, OH, and C(2), as well as atomic C and H, are observed when a femtosecond filament is formed in the laminar ethanol/air flame on an alcohol burner. The fluorescence signals of these species are found to vary as functions of the position of interaction of the filament with the flame along the vertical axis of the central combusting flow, opening up a possibility for remote combustion diagnostic in engines by the excitation of femtosecond laser filament.

Covalent Functionalization of Graphene with Reactive Intermediates

Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations warrant comprehensive studies. The availability of well-defined pristine graphene starting materials in large quantities remains a key obstacle to the advancement of synthetic graphene chemistry.

Static hyperpolarizability of the van der Waals complex CH4N2

The static first hyperpolarizability of the van der Waals CH(4)-N(2) complex was calculated. The calculations were carried out in the approximation of the rigid interacting molecules for a broad range of intermolecular separations (R = 6-40 a(0)) and for six configurations at CCSD(T) level of theory using the correlation consistent aug-cc-pVTZ basis set with the basis set superposition error correction. It was shown that the long-range classical approximation, including the terms up to R(-6), is in a good agreement with ab initio calculations for R > 11 a(0). It was found out that for the family of most stable configurations of the complex, the first hyperpolarizability invariants practically do not change (the changes are less than 0.1%). Under forming the stable van der Waals CH(4)-N(2) complex, the intensity and degree of depolarization of the hyper-Rayleigh scattering are noticeable decreased (by ∼10%) to be compared with the free CH(4) and N(2) molecules.

Role of Interfacial Charge Transfer State in Charge Generation and Recombination in Low-Bandgap Polymer Solar Cell

The charge carrier dynamics in blend films of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was studied by transient absorption spectroscopy in order to address the origin of limited external quantum efficiency (EQE) of this solar cell compared to that of a benchmark solar cell composed of regioregular poly(3-hexythiphene) (RR-P3HT) and PCBM. Upon photoexcitation, PCPDTBT singlet excitons promptly convert to the interfacial charge transfer (CT) state that is a Coulombically bound charge pair of PCPDTBT polaron and PCBM anion at the heterojunction with almost 100% efficiency in a picosecond. In other words, the exciton diffusion efficiency ηED and charge transfer efficiency ηCT are 100% in this blend, which are higher than and comparable to those of the RR-P3HT/PCBM solar cell, respectively. On a time scale of nanoseconds, 70% of the PCPDTBT bound polarons are dissociated into free ch...

In vitro biocompatibility and mucoadhesion of montmorillonite chitosan nanocomposite: A new drug delivery

A “Clay Bio Polymer Nanocomposite” (CBPN) to be used in drug release was prepared by dispersion of montmorillonite (Mt) particles in chitosan (Ch) solution. The obtained hybrid material was characterized for in vitro biocompatibility on Caco-2 cell cultures. Cytotoxicity and cell proliferation of the nanocomposite were tested, comparing results with free Ch and Mt. Cell proliferation was assessed both by WST-1 test and wound-healing measurements by means of Image Analysis Software. The last method is a proof of concept test that has the advantage of direct visualization and quantification of cell growth. Nanocomposite was also characterized for hydration (water uptake) pattern and mucoadhesive properties, which were considered as important features for the application of this material in modified release systems. Results showed that the prepared CBPN showed good biocompatibility in the range 5–500 μg/ml, being also able to effectively stimulate cell proliferation. Moreover, nanocomposite possessed mucoadhesive properties combined with low solubility in acidic environment. We conclude that interaction between Ch and Mt produced a new biohybrid material that can be considered as promising candidate for modified drug delivery formulations.

On the equilibrium structures of the complexes H2C3H+·Ar and c-${\rm C}_{\rm 3} {\rm H}_{\rm 3}^{\rm + }$C3H3+·Ar: Results of explicitly correlated coupled cluster calculations

Explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level [T. B. Adler et al., J. Chem. Phys. 127, 221106 (2007)] has been employed in a study of the potential energy surfaces for the complexes H(2)C(3)H(+) · Ar and c-C(3)H(3)(+) · Ar. For the former complex, a pronounced minimum with C(s) symmetry was found (D(e) ≈ 780 cm(-1)), well below the local "H-bound" minimum with C(2v) symmetry (D(e) ≈ 585 cm(-1)). The absorption at 3238 cm(-1) found in the recent infrared photodissociation spectra [A. M. Ricks et al., J. Chem. Phys. 132, 051101 (2010)] is, thus, interpreted as an essentially free acetylenic CH stretching vibration of the propargyl cation. A global minimum of C(s) symmetry was also obtained for c-C(3)H(3)(+) (D(e) ≈ 580 cm(-1)), but the energy difference with respect to the local C(2v) minimum is only 54 cm(-1).

Weak interactions in ion–ligand complexes of C3H+3 isomers: competition between H-bound and C-bound structures in c-C3H+3·L and H2CCCH+·L (L = Ne, Ar, N2, CO2, and O2)

Explicitly correlated coupled cluster theory at the CCSD(T)-F12x level (T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys.127, 221106, 2007) has been employed to study structures and vibrations of complexes of type c-C(3)H(3)(+)·L and H(2)C(3)H(+)·L (L = Ne, Ar, N(2), CO(2), and O(2)). Both cations have different binding sites, allowing for the formation of weak to moderately strong hydrogen bonds as well as "C-bound" or "π-bound" structures. In contrast to previous expectations, the energetically most favourable structures of all H(2)C(3)H(+)·L complexes investigated are "C-bound", with the ligand bound to the methylenic carbon atom. The theoretical predictions enable a more detailed interpretation of infrared photodissociation (IRPD) spectra than was possible hitherto. In particular, the bands observed in the range 3238-3245 cm(-1) (D. Roth and O. Dopfer, Phys. Chem. Chem. Phys.4, 4855, 2002) are assigned to essentially free acetylenic CH stretching vibrations of the propargyl cation in "C-bound" H(2)C(3)H(+)·L complexes.

I − ⋅ CH 3 X (X=Cl,Br,I) photodetachment: The effect of electron-molecule interactions in cluster anion photodetachment spectra and angular distributions

The electron kinetic energy dependence of the photoelectron spectra and angular distributions of I(-)⋅CH(3)X (X=Cl,Br,I) cluster anions are measured via velocity mapped imaging at wavelengths between 350 and 270 nm. Processes analogous to those encountered in free CH(3)X-electron interactions are revealed. In particular, the presence and energies of resonances associated with a low lying σ(∗) state have a marked effect on the results of I(-)⋅CH(3)X photoexcitation. These effects (vibrational excitation, product anion production, and alteration of the photoelectron angular distribution) are far more prominent for I(-)⋅CH(3)I. However, in the vicinity of the (2)P(1/2) threshold there is a sharp deviation in the (2)P(3/2) channel angular distribution and an enhancement of the (2)P(3/2) channel vibrational structure of all three cluster anions. These latter effects are specific to the cluster anion environment through the relaxation of the partner excited I atom and subsequent electronic autodetachment.

DFT and direct ab-initio MD study on hyperfine coupling constants of methyl radicals adsorbed on model surface of silica gel

Methyl radicals interacting with silica gel surfaces have been investigated by means of DFT and direct ab-initio molecular dynamics (MD) methods using cluster models. Four typical binding sites of CH 3 on the cluster models were found in the geometry optimization from several initial geometries of CH 3 around the silica gel clusters. These were two silanol Si–OH sites and two siloxane Si–O–Si sites. In both sites, magnitude of hyperfine coupling constants of the methyl radical ( a H) was smaller than that of free CH 3 ( a H = 23.04 G). Temperature effects on a H of the methyl radical were investigated by means of the direct ab-initio MD method. The hyperfine coupling constant of CH 3 interacting with the SiOH group decreased with increasing temperature. The methyl radical interacting with alkali metal supported silica gel was also investigated for comparison. The electronic states of methyl radicals on silica gel were discussed on the basis of theoretical results.

Vinylphosphine-borane: Synthesis, gas phase infrared spectroscopy, and quantum chemical vibrational calculations

Both experimental and theoretical investigations are reported on the infrared spectrum of vinylphosphine-borane (CH(2)=CHPH(2) x BH(3)), a donor-acceptor complex. The gas phase infrared spectra (3500-600 cm(-1)) have been recorded at 0.5 cm(-1) resolution. This first primary alpha,beta-unsaturated phosphine-borane synthesized up to now is kinetically very unstable in the gas phase and decomposes rapidly into two fragments: the free vinylphosphine CH(2)=CHPH(2) and the monoborane BH(3) which dimerizes to form the more stable diborane B(2)H(6). Spectra of free CH(2)=CHPH(2) and B(2)H(6) compounds were also recorded to assign some vibration modes of the complex in very dense spectral regions. The analysis was completed by carrying out quantum mechanical calculations by density functional theory method at the B3LYP/6-31+G(**) level. Anharmonic frequencies and infrared intensities of the two predicted gauche and syn conformers of the vinylphosphine-borane complex were calculated in the 3500-100 cm(-1) region with the use of a variational approach, implemented in the P_ANHAR_V1.2 code. Because of the relatively weak interaction between the vinylphosphine and the monoborane, the vibrations of the complex can easily be subdivided into modes localized in the CH(2)=CHPH(2) and BH(3) moieties and into "intermolecular" modes. Localized modes are unambiguously correlated with the modes of the isolated monomers. Therefore, they are described in terms of the monomer vibrations, and the complexation shifts are defined as Delta nu = nu(complex) - nu(monomer) to make the effect of the complexation precise on each localized mode. In this objective, anharmonic frequencies and infrared intensities of the BH(3) monomer and the stable gauche and syn conformers of the free vinylphosphine were obtained at the same level of theory. In the gas phase, only the syn form of the complex was observed and assigned. All theoretically predicted frequencies and complexation shifts in magnitude and direction are in good agreement with experiment. By infrared spectroscopy assisted by quantum chemical calculations, the consequences of the complexation of an alpha,beta-unsaturated phosphine by borane on the physicochemical properties of the formed 12-atom complex have been efficiently evaluated.