Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

Studies of phase transitions and ferroelastic domain walls in Pb5Al3F19 crystals by optical measurements

Three phase transitions between 100 and 400 K were previously shown by X-ray diffraction measurements. Such results have been confirmed by optical measurements on crystals. The thermal dependence of the birefringence has been determined. A new phase transformation has been shown at around 590 K not only by optical study but also by dielectric measurements. Ferroelastic domain-walls have been visualized. The sequence transition has been discussed taking into account the various space groups.     

Reinvestigation of the ν2 + 2ν3 subband in the overtone icosad of 12CH4 using cavity ring-down (CRD) spectroscopy of a supersonic jet expansion

We report a detailed reinvestigation of the ν₂?+?2ν₃ combination band of methane ¹²CH₄ centred at (7510.3378?±?0.003)?cm^?1 ((225.154263?±?0.0001)?THz) within the icosad of the overtone absorption. A new experimental setup is described, allowing us to carry out cw-laser cavity ring-down spectroscopy (cw-CRDS) at instrumental resolution in the MHz range in seeded supersonic jet expansions down to rotational temperature of 7?K compared to previous cw-CRDS measurements in our group achieving about 50?K in expansions of neat CH₄. We provide a careful re-analysis on the basis of our new experimental results for the Q and R branch transitions including data obtained between about 7 and 300?K under various conditions. We resolve previously observed discrepancies of assignments and are able to present a definitive assignment for lines involving angular momentum quantum numbers up to J?=?4. The analysis of relative intensities in spectra taken at rotational and effective translational temperatures between about 50?K and less than 10?K indicate conservation of nuclear spin symmetry upon supersonic jet expansion, in agreement with previous results using other techniques and covering other spectral ranges.     

功率对氘代辉光放电聚合物结构和力学性能的影响

采用射频辉光放电聚合技术,在低压等离子体聚合装置上开展在5~20 W功率下氘代辉光放电聚合物薄膜的制备及性能研究。利用傅里叶变换红外吸收光谱仪表征薄膜的化学结构,讨论了功率变化对其官能团结构的影响规律。利用元素分析仪和纳米压痕仪表征薄膜中氘原子的相对含量和薄膜的力学性能。研究表明:随着功率的升高,薄膜中的氘含量先升高后降低,在10W时达到最大,薄膜中SP3 CD的相对含量增加,SP3 CD2的相对含量减小;聚合物薄膜的硬度和杨氏模量均随功率的增加而减小。     

Spectral tuning of InGaAs/GaAs quantum dot infrared photodetectors with bandpass guided‐mode resonance filters

Quantum dot infrared photodetectors can be coupled with micro‐structured filters to create narrowband sensors. Guided‐mode resonance filters based on a high‐index dielectric slab can exhibit bandpass characteristics that are suitable for monolithic integration with focal‐plane arrays. Here, patterned Ge filters were integrated with InGaAs/GaAs quantum dot detectors to linearly tune their 77 K photoresponse peaks from 5.6 µm to 6.2 µm. The dark current was not influenced by these filters but the ability to narrow the photoresponse linewidth was limited by substrate scattering, which is often encountered with front‐side illumination architectures. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Good match exploration for thermal infrared face recognition based on YWF-SIFT with multi-scale fusion

Stable local feature detection is a critical prerequisite in the problem of infrared (IR) face recognition. Recently, Scale Invariant Feature Transform (SIFT) is introduced for feature detection in an infrared face frame, which is achieved by applying a simple and effective averaging window with SIFT termed as Y-styled Window Filter (YWF). However, the thermal IR face frame has an intrinsic characteristic such as lack of feature points (keypoints); therefore, the performance of the YWF-SIFT method will be inevitably influenced when it was used for IR face recognition. In this paper, we propose a novel method combining multi-scale fusion with YWF-SIFT to explore more good feature matches. The multi-scale fusion is performed on a thermal IR frame and a corresponding auxiliary visual frame generated from an off-the-shelf low-cost visual camera. The fused image is more informative, and typically contains much more stable features. Besides, the use of YWF-SIFT method enables us to establish feature correspondences more accurately. Quantitative experimental results demonstrate that our algorithm is able to significantly improve the quantity of feature points by approximately 38%. As a result, the performance of YWF-SIFT with multi-scale fusion is enhanced about 12% in infrared human face recognition.     

Structural, optical and electromagnetic properties of aluminum-clay nanocomposites

Aluminum pillared and exchanged bentonite particles were synthesized by the ion exchange method. The characteristics of the particles were investigated by Fourier-transform infrared spectra (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), scanning electron microscope (SEM), electron dispersive X-ray spectrometer (EDS), reflectance spectrophotometer (RS) and electromagnetic transition instrument (ETI). FTIR spectra showed a successful incorporation of Al complexes into the clay interlayer. The TGA result demonstrated an improvement in thermal stability of the Al-pillared clay compared with the untreated particles. SEM and EDX results showed the presence of aluminum aggregates on the surface of clay. It was also found that Al ions affect electromagnetic properties of the clay particles.     

Oxygen consumption and chemisorption in low-temperature oxidation of sub-bituminous pulverized coal

Studying the effect of oxygen in coal oxidation is very important for understanding and controlling coal spontaneous combustion. However, the oxygen effect is not very easy to determine clearly due to the large effect of heat source on coal oxidation in temperature rising experiments. Here, focused on sub-bituminous coal, the oxygen effect was separated from coal oxidation by continuously measuring FTIR spectra of coal with respect to varying temperatures and under oxygen and nitrogen. The active groups’ real-time changes of coal oxidation, thermal treatment and oxygen effect were measured. The carboxylic ester and carboxyl units are the main functional groups that increase with temperatures increasing under oxygen and nitrogen, while the other functional groups decrease in quantity. The oxygen effect promoted the consumption of aliphatic hydrocarbons and hydroxyl groups and also promoted the formation of oxygen-containing groups (except hydroxyl). Four characteristic temperature stages involved in the oxygen effect and their key functional groups were identified. Simultaneously, the relationship of oxygen consumption and chemisorption in oxygen effect was analyzed. The starting temperature of oxygen chemisorption is between 50 and 60°C. The maximum contribution of oxygen effect was observed in methyl and methylene groups. These results are important for chemical control of coal spontaneous combustion. The oxidation of aliphatic hydrocarbon should be controlled before oxygen chemisorption. The value of oxygen consumption between 70 and 80°C can be measured accurately due to the constant chemisorption rate, which help to identify the tendency for spontaneous combustion. These results will help in better understanding of the reaction mechanism of coal oxidation, especially the oxygen effect.     

Influence of the degree of ionization on the growth mechanism of poly(diallyldimethylammonium)/poly(acrylic acid) multilayers

pH‐dependent growth laws of the mass coverage Γ(n) of poly(diallyldimethylammonium) chloride and poly(acrylic acid) (PAA) layer‐by‐layer films are analyzed by Quartz Crystal Microbalance‐D. (Attenuated Total Reflection)‐FTIR spectroscopy shows a degree of dissociation of acrylic acid groups in the films identical to that in solution. Apart from pH‐regimes of differently pronounced exponential and linear growth, the corresponding kinetics indicate pH‐dependent adsorption, reorganization, and diffusion processes. As the thickest films form with almost uncharged PAA (low pH), the results can only partly be explained by the dissociation degree of PAA in the film. For intermediate and high pH values chain interdiffusion as a mechanism for nonlinear growth is strongly dependent on the charge density of the PAA chains. However, at low pH other types of interactions, most likely ion–dipole interactions, play a major role in the multilayer growth. Furthermore, a change in the symmetry of growth can be observed in the low to intermediate pH range. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 425–434