Towards Understanding Excited-State Properties of Organic Molecules Using Time-Resolved Soft X-ray Absorption Spectroscopy

The extension of the pump-probe approach known from UV/VIS spectroscopy to very short wavelengths together with advanced simulation techniques allows a detailed analysis of excited-state dynamics in organic molecules or biomolecular structures on a nanosecond to femtosecond time level. Optical pump soft X-ray probe spectroscopy is a relatively new approach to detect and characterize optically dark states in organic molecules, exciton dynamics or transient ligand-to-metal charge transfer states. In this paper, we describe two experimental setups for transient soft X-ray absorption spectroscopy based on an LPP emitting picosecond and sub-nanosecond soft X-ray pulses in the photon energy range between 50 and 1500 eV. We apply these setups for near-edge X-ray absorption fine structure (NEXAFS) investigations of thin films of a metal-free porphyrin, an aggregate forming carbocyanine and a nickel oxide molecule. NEXAFS investigations have been carried out at the carbon, nitrogen and oxygen K-edge as well as on the Ni L-edge. From time-resolved NEXAFS carbon, K-edge measurements of the metal-free porphyrin first insights into a long-lived trap state are gained. Our findings are discussed and compared with density functional theory calculations.     

Nondestructive Evaluation of Thermal Barrier Coatings Using Impedance Spectroscopy

This article reviews previous studies on nondestructive evaluation of thermal barrier coatings (TBCs) using impedance spectroscopy (IS). IS or electrochemical impedance spectroscopy has been widely used to measure the electrical properties of materials and electrochemical behavior at electrode/electrolyte interfaces. TBCs, which comprise metallic and ceramic multilayers, have been widely used in the hot section of aeroturbine engines to increase turbine efficiency and to extend the life of metallic components. Since 1999, IS has been developed to examine degradation of the TBCs as a nondestructive evaluation tool, which is critical for prediction of TBCs lifetime during service. IS has been used both at high temperature in dry environments and in aqueous solutions. Impedance spectra of TBCs reflect change in TBC thickness, porosity, cracks, sintering, and yttria-stabilized zirconia phase transformation. Meanwhile, impedance measurements indicate the thermally grown oxide growth and the failure in TBCs. In addition, the thermal conductivity of TBCs can be correlated to impedance measurement results.     

Application of Time-Resolved Fluorescence Spectroscopy on the Analysis of PAH-Coated Aerosols

A fiberoptic sensor system was developed for the detection of PAH-coated aerosols. It incorporates a pulsed nitrogen laser for excitation and a monochromator, a photomultiplier and a digital storage oscilloscope for recording of fluorescence decay curves. With a software-realized photon counting technique detection limits less than 100 ng/m³ for most of the PAHs investigated were achieved with NaCl as a substrate (e.g., 20 ng/m³ for benzo(e)pyrene on NaCl). The sensitivity of the system decreased dramatically when PAH adsorbed on carbon aerosol were analyzed. With pyrene on polydisperse NaCl aerosol the formation of excimers was observed and the formation kinetic could be analyzed. With benzo(e)pyrene on NaCl under similar conditions excimer fluorescence was observed but not the formation kinetic. This indicates the formation of micro-crystals of PAHs on aerosol surfaces even at surface coverages Θ ?1. Due to the observed matrix effects experiments were carried out, at which the PAHs were thermally desorbed in advance of the analysis. By this PAH fluorescence was measurable with carbon as matrix.     

Dynamical Studies of Zeolitic Protons and Adsorbates by Picosecond Infrared Spectroscopy

The application of (picosecond) nonlinear infrared spectroscopy to investigate zeolite catalysts and adsorbates is reviewed. In these time-resolved experiments, one specific vibration in the zeolite system (i.e., a zeolite or adsorbate vibration) is selectively excited with an ultrashort (tunable) mid-infrared pulse. The effect of this excitation and the subsequent energy relaxation can be monitored real time, providing information on the structure of the bare zeolite and adsorption complexes. More importantly, with this technique the picosecond energy flow at the catalytic site and the dynamics of the catalyst-adsorbate interaction can be investigated: Short-lived transient species (e.g., reaction intermediates) are observed and the picosecond relaxation rates and pathways at the catalytic site render insights into the dynamics of the interaction between the zeolite catalyst and its adsorbates at a molecular level. This illustrates the potential of time-resolved infrared spectroscopy in the investigations of catalytic systems.     

Dynamical Studies of Zeolitic Protons and Adsorbates by Picosecond Infrared Spectroscopy

The application of (picosecond) nonlinear infrared spectroscopy to investigate zeolite catalysts and adsorbates is reviewed. In these time-resolved experiments, one specific vibration in the zeolite system (i.e., a zeolite or adsorbate vibration) is selectively excited with an ultrashort (tunable) mid-infrared pulse. The effect of this excitation and the subsequent energy relaxation can be monitored real time, providing information on the structure of the bare zeolite and adsorption complexes. More importantly, with this technique the picosecond energy flow at the catalytic site and the dynamics of the catalyst-adsorbate interaction can be investigated: Short-lived transient species (e.g., reaction intermediates) are observed and the picosecond relaxation rates and pathways at the catalytic site render insights into the dynamics of the interaction between the zeolite catalyst and its adsorbates at a molecular level. This illustrates the potential of time-resolved infrared spectroscopy in the investigations of catalytic systems.     

Picosecond Resonance Coherent Anti-Stokes Raman Spectroscopy of Light- and Dark-Adapted Bacteriorhodopsin

Coherent anti-Stokes Raman scattering (CARS) from the C=C stretching band region of retinal, recorded with low-power, 7-ps (fwhm) laser excitation selected to be in electronic resonance with the retinal chromophore, is presented for light- and dark-adapted bacteriorhodopsin (BR) samples. By minimizing photochemistry with low-power excitation, the picosecond resonance CARS (PR/CARS) spectrum of BR-570 (13-trans, 15-anti-retinal) is obtained directly from the light-adapted BR sample. The PR/CARS spectrum of BR-548 (13-cis, 15-syn retinal) is derived from a quantitative analysis of PR/CARS data from dark-adapted BR which contains comparable amounts of BR-570 and BR-548. Band origin positions, lineshapes, relative intensities, and phase factors describing the electronic resonances are obtained from a quantitative fit of the PR/CARS spectra to third-order susceptibility (χ⁽³⁾) relationships. These PR/CARS data, the first reported for a molecular system as large as BR, demonstrate the experimental viability of CARS for recording the vibrational spectrum of a chromophore within a trans-membrane protein. In addition, the χ⁽³⁾ analysis shows that a CARS spectrum of a mixture of isomeric chromophores can be quantitatively separated into CARS data assignable to its individual components. The significance of these results with respect to analyzing picosecond time-resolved CARS data from intermediates in the BR photocycle is discussed.     

In-Situ Measurement of the Stress-Induced Phase Transformations in Magnesia-Partially-Stabilized Zirconia Using Raman Spectroscopy

Raman spectroscopy has been used to examine the connection between room-temperature creep and stress-induced phase transformations in TS-Grade Mg-PSZ. The in-situ phase measurements obtained show that the tetragonal phase transforms to both the orthorhombic and monoclinic structures under stress. The effect of precipitate orientation is indicated by the variation of creep strain with monoclinic volume fraction.     

Measurement of Micro Kinetics of Hydrogenation in Liquid Phase Using Raman Spectroscopy

Hydrogenation of liquid organic hydrogen carriers is usually carried out in liquid phase. To measure the kinetics of this hydrogenation, an experimental setup using in situ Raman spectroscopy for analysis of the reaction mixture is proposed. With this setup it is possible to perform hydrogenation reactions at temperatures of up to 573 K and pressures up to 25 MPa. For validation of the experimental setup the hydrogenation of 1‐octene was measured in liquid phase. The reaction progress can be monitored in detail by Raman spectroscopy. To determine kinetic parameters from the experimental data, two modeling approaches were applied: a classic kinetic model and a thermodynamic kinetic model. The results were compared to literature data.     

Solvent Characterization Using the Dispersion Number

Abstract

When developing new solvent extraction processes, one often has to evaluate new solvents, new aqueous phases, or both for their ability to work in plant-scale equipment. To facilitate solvent characterization, a simple test is proposed based on the dimensionless dispersion number (N_Di). It allows one to characterize the ability of the solvent to separate from a two-phase dispersion and to estimate process throughput for equipment of a given size. Several ways to carry out the N_Di test are given, including a standard test procedure. The N_Di test was applied to the performance of solvent extraction equipment with discrete process stages, the leaching of plasticizers from plastic tubing, and the development of a new solvent for the combined extraction of strontium and transuranic elements.     

Multifunctional Shape-Stabilized Phase Change Materials with Enhanced Thermal Conductivity and Electromagnetic Interference Shielding Effectiveness for Electronic Devices

A paraffin-based shape-stabilized composite phase change material (CPCM) is fabricated with dramatically enhanced thermal conductivity and excellent electromagnetic interference (EMI) shielding capacity. The as-prepared CPCMs are supported by graphene-based frameworks with many bubble-like micropores that are prepared by the addition of polystyrene microspheres into graphene oxide hydrogel as hard templates. These bubble-like micropores can encapsulate paraffin wax (PW) due to the strong capillary force between the graphene-based framework and PW and leading to enhanced shape stability of the as-prepared CPCMs. Moreover, the continuous thermally and electrically conductive network formed by graphene nanoplatelets endows the as-prepared CPCMs with a high thermal conductivity and an excellent EMI shielding effectiveness. When the ratio of graphene-based framework is 23.0 wt%, the thermal conductivity and latent heat of CPCM reaches 28.7 W m⁻¹ k⁻¹ and 175.8 J g⁻¹, respectively, and the EMI shielding effectiveness is higher than 45 dB in the frequency of 8.2–12.4 GHz. Their outstanding thermal and EMI shielding performance makes the as-prepared CPCMs promising candidates for use in thermal management and EMI shielding of electronic devices.     

Intramolecular Charge Transfer of Curcumin and Solvation Dynamics of DMSO Probed by Time-Resolved Raman Spectroscopy

Intramolecular charge transfer (ICT) of curcumin in dimethyl sulfoxide (DMSO) solution in the excited state was investigated by femtosecond electronic and vibrational spectroscopy. Excited-state Raman spectra of curcumin in the locally-excited and charge-transferred (CT) state of the S₁ excited state were separated due to high temporal (<50 fs) and spectral (<10 cm⁻¹) resolutions of femtosecond stimulated Raman spectroscopy. The ultrafast (0.6–0.8 ps) ICT and subsequent vibrational relaxation (6–9 ps) in the CT state were ubiquitously observed in the ground- and excited-state vibrational modes of the solute curcumin and the ν_CSC and ν_S=O modes of solvent DMSO. The ICT of curcumin in the excited state was preceded by the disruption of the solvation shells, including the breakage of hydrogen bonding between curcumin and DMSO molecules, which occurs at the ultrafast (20–50 fs) time scales.     

液-液-液三相体系的相分散与分相特性

以包含双油相和单水相的液-液-液三相体系为对象,利用编程控制的CCD照相系统,考察了搅拌槽内不同操作条件下液-液-液三相体系的相分散及分相情况. 实验结果表明,桨型对三相体系的分散情况有较大影响,径流桨的分散效果优于轴流桨,下推式轴流桨优于上推式轴流桨;各相体积比的改变会导致不同的相分散形式;不同相分散形式的分相过程也不相同,实验中体系的分相过程可以分为凝并界面水平型与无规则型两种典型情况,分别对应两种不同的相分散形式;采用分相数学模型,可成功预测凝并界面水平型分相过程中各界面的高度随时间的变化.     

Characterization of Phase Separation and Thermal History Effects in Magnesium Silicate Glass Fibers by Nuclear Magnetic Resonance Spectroscopy

Liquid–liquid immiscibility, leading to the separation of silica-rich and silica-poor domains, is a common phenomenon in binary silicate glasses, but can be difficult to detect and characterize when rapid cooling results in nano-scale domain dimensions. ²⁹Si nuclear magnetic resonance (NMR) spectroscopy can be very useful for detecting such phase separation, because the exclusion of paramagnetic impurity ions from the silica-rich regions can greatly slow their spin-lattice relaxation rates. Properly designed experiments can therefore largely isolate the NMR signals from high-silica and low-silica domains, and thus provide information about their proportions, compositions, and short- to intermediate-range structures. We demonstrate this approach here for fiber glasses that are predominantly magnesium, or calcium-magnesium silicates, with minor contents of alumina. For bulk compositions within the known region of stable liquid immiscibility, phase separation occurs even when extremely rapid cooling yields fibers less than 1 μm in mean diameter. Slower cooling increases the extent of separation, while the addition of small amounts of alumina reduces it.     

Effect of Mn Dispersion on Gas Phase Ozone Decomposition at Room Temperature Using Natural Manganese Oxides

In this study, various analyses were performed to evaluate the ozone removal characteristics using natural manganese ore (NMO) at room temperature. NMO exists primarily in the form of MnO₂, and the specific forms of manganese oxide are formed as the calcination temperature increases. The activity tests, XRD, BET, and XPS analyses confirmed that the dispersion of manganese site exposed to the surface was a critical factor for ozone removal using NMO. To evaluate the actual application of NMO as a catalyst for ozone decomposition, NMO was also made as a form of monolith; as a result, the catalyst showed an excellent conversion rate (over 80%) even at space velocity 30,000 h^?1.     

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Hygroscopicity and phase transitions were measured with deposited particles of ammonium sulfate (AS), ammonium nitrate (AN), malonic acid (MA), glutaric acid (GA), glyoxylic acid (GlyA), as well as two mixed particle systems AS-MA and AS-GA using micro-Raman spectroscopy. Hygroscopicity was presented in terms of water-to-solute mass ratios, which were obtained from the integrated area ratios of the Raman water band to a distinct solute peak. Deliquescence and crystallization were confirmed by abrupt changes in the Raman peak positions and the full-width-half-heights of distinct solute peaks. The results for AS, AN, MA, and GA agreed well with literature reports and model predictions. For GlyA, we detected the Raman water band at near 0% RH, indicating that the spectral technique is sensitive for hygroscopic measurements at very low RH. Additional spectral feature at ～ 0% RH was also observed. In the case of more complicated AS-dicarboxylic acid mixed systems, the partial phase transitions of the organic components were identified using the intensity ratios of aqueous to solid C = O peaks. AS-MA particles did not completely crystallize and gradual water uptake with increasing RH from 3% was observed. Moreover, it was found that AS-GA particles showed step-wise crystallization in which the AS fraction crystallized prior to the GA fraction. The measured water content and complete DRH of both mixed systems were consistent with the published values. The results show the utility of micro-Raman spectroscopic analysis in studying hygroscopicity and phase characterizations of the chemical species in mixed particles.     

Longitudinal Dispersion of the Continuous Phase in Spray Extraction Columns

Longitudinal dispersion of the continuous phase was studied in spray extractors operated in the loose, close, and turbulized drop packing modes. The Peclet number was found to depend on the Reynolds number modified to take into account the hydrodynamic conditions in the working zone of the column. When the continuous phase is pulsed, the Peclet number is also governed by the modified Reynolds number, which accounts for the effect of pulsation on the longitudinal dispersion.     

Longitudinal Dispersion of the Dispersed Phase in Spray Extraction Columns

Theoretical Foundations of Chemical Engineering -     

Continuous Selective Heating of the Solid Phase of a Dispersion

A new technique is suggested for the continuous and selective heating of the solid phase in a flowing dispersion. This technique is implemented in a heater–valve-pulsed apparatus unit. Mathematical models are developed for the cocurrent and countercurrent designs of the heater. Analytical solutions are obtained for the model equations, and parameters governing the continuous selective heating of the solid phase are determined. A design algorithm is suggested for the unit.     

不溶性硫黄热稳定性和分散性及其评价方法

介绍不溶性硫黄（IS）的热稳定性和分散性及其评价方法,总结了不同测试评价方法的差异。IS热稳定性分析以恒温油浴过滤法为主,但是测定结果受测试用矿物油、设备以及操作因素等的影响较大,开发在更大程度上利用仪器测试的方法是未来IS热稳定性分析的发展方向。IS分散性测定目前尚没有统一的标准,研究制定科学有效的分散性测试标准是IS生产企业和轮胎企业共同的需求和任务。