Broadband Multidimensional Spectroscopy Identifies the Amide II Vibrations in Silkworm Films

We used two-dimensional infrared spectroscopy to disentangle the broad infrared band in the amide II vibrational regions of Bombyx mori native silk films, identifying the single amide II modes and correlating them to specific secondary structure. Amide I and amide II modes have a strong vibrational coupling, which manifests as cross-peaks in 2D infrared spectra with frequencies determined by both the amide I and amide II frequencies of the same secondary structure. By cross referencing with well-known amide I assignments, we determined that the amide II (N-H) absorbs at around 1552 and at 1530 cm^–1 for helical and β-sheet structures, respectively. We also observed a peak at 1517 cm⁻¹ that could not be easily assigned to an amide II mode, and instead we tentatively assigned it to a Tyrosine sidechain. These results stand in contrast with previous findings from linear infrared spectroscopy, highlighting the ability of multidimensional spectroscopy for untangling convoluted spectra, and suggesting the need for caution when assigning silk amide II spectra.     

Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine

Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λ_ex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λ_ex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes.     

All-Polymer Piezo-Composites for Scalable Energy Harvesting and Sensing Devices

Silicone elastomer composites with piezoelectric properties, conferred by incorporated polyimide copolymers, with pressure sensors similar to human skin and kinetic energy harvester capabilities, were developed as thin film (<100 micron thick) layered architecture. They are based on polymer materials which can be produced in industrial amounts and are scalable for large areas (m²). The piezoelectric properties of the tested materials were determined using a dynamic mode of piezoelectric force microscopy. These composite materials bring together polydimethylsiloxane polymers with customized poly(siloxane-imide) copolymers (2–20 wt% relative to siloxanes), with siloxane segments inserted into the structure to ensure the compatibility of the components. The morphology of the materials as free-standing films was studied by SEM and AFM, revealing separated phases for higher polyimide concentration (10, 20 wt%). The composites show dielectric behavior with a low loss (<10⁻¹) and a relative permittivity superior (3–4) to pure siloxane within a 0.1–10⁶ Hz range. The composite in the form of a thin film can generate up to 750 mV under contact with a 30 g steel ball dropped from 10 cm high. This capability to convert a pressure signal into a direct current for the tested device has potential for applications in self-powered sensors and kinetic energy-harvesting applications. Furthermore, the materials preserve the known electromechanical properties of pure polysiloxane, with lateral strain actuation values of up to 6.2% at 28.9 V/μm.     

Hemocompatibile Thin Films Assessed under Blood Flow Shear Forces

The aim of this study was to minimize the risk of life-threatening thromboembolism in the ventricle through the use of a new biomimetic heart valve based on metal–polymer composites. Finite volume element simulations of blood adhesion to the material were carried out, encompassing radial flow and the cone and plane test together with determination of the effect of boundary conditions. Both tilt-disc and bicuspid valves do not have optimized blood flow due to their design based on rigid valve materials (leaflet made of pyrolytic carbon). The main objective was the development of materials with specific properties dedicated to contact with blood. Materials were evaluated by dynamic tests using blood, concentrates, and whole human blood. Hemostability tests under hydrodynamic conditions were related to the mechanical properties of thin-film materials obtained from tribological tests. The quality of the coatings was high enough to avoid damage to the coating even as they were exposed up to maximum loading. Analysis towards blood concentrates of the hydrogenated carbon sample and the nitrogen-doped hydrogenated carbon sample revealed that the interaction of the coating with erythrocytes was the strongest. Hemocompatibility evaluation under hydrodynamic conditions confirmed very good properties of the developed coatings.     

热力联合作用弹性薄圆板的弯曲与屈曲

导出了热力联合作用下弹性薄圆板的弯曲动力响应控制方程,讨论了其弯曲变形特点及影响失效的因素。分析表明在短时热能沉积作用下,热屈曲是弹性薄板失效的主要方式之一;反鼓包或反冲塞是热屈曲的后继行为;增加外载和热能沉积功率水平都将加速热屈曲的发生;材料的温度相关性与热能沉积的时空分布对薄板的力学行为都有重要影响,同为产生和影响热剪切失效(反冲塞)的重要因素。     

电子束、离子辅助和离子束溅射三种工艺对光学薄膜性能的影响

运用电子束、离子辅助和离子束溅射三种镀膜工艺分别制备光学薄膜,包括单层氧化物薄膜和增透膜,然后采取一系列测试手段,如Zygo轮廓仪、原子力显微镜、表面热透镜技术和X射线衍射等技术,来分析和研究不同的工艺对这些薄膜性能的不同影响,以判断合理的沉积工艺。     

电子碰撞引起的铜元素K壳层电离截面的测量与修正

在电子碰撞的情形下,通过对铜靶的特征X射线测量,从而推算出它的K壳层电离截面。在实验中采用了薄靶厚衬底新方法。通过电子输运计算,由厚衬底产生的反射电子对计数的影响得以修正。用蒙特卡罗技术对质量厚度为23 mg∕cm2的铜靶的多次散射影响作了修正。     

关于制备1315nm 45°入射高反射镜的实验研究

从优化膜系、控制膜厚、改善膜面、均衡应力等四个方面开展了实验研究工作,为制备1315nm 45°高反射镜提供一些判断实验数据,并提出改进的方法,从而使制备的高反射膜取得满意的结果：反射率大于99.8%。     

铜铟镓硒薄膜光伏组件中电池与封装材料界面的光学特性对组件性能的影响

根据测试数据,分析模拟了铜铟镓硒(CIGS)薄膜光伏组件中电池的活性区域、非活性区域与封装材料之间界面的光学特性对组件的短路电流产生的影响。根据组件结构建立了光学模型,从光学模拟结果分析组件内的反射与吸收。发现电池前电极透明导电氧化物薄膜(TCO)与封装材料界面的反射不可忽视,提出通过在透明导电氧化物薄膜与封装材料之间添加减反射层,并以MgO作为膜层材料以降低活性区域的界面反射;模拟了在非活性区域一次反射光角度与二次反射的关系,由此分析了非活性区域反射面倾角、镜面反射与漫反射比例对光利用的影响。模拟结果显示,活性区域的减反层结构可降低透明导电氧化物薄膜表面的反射率1%以上,而通过在非活性面积区域制备光反射结构,理论上能够利用非活性区域光照超过50%。     

α-C∶H膜化学结构对光学性能的影响

选用体积分数为99.999 9%的H2及反式-2-丁烯（T2B）为工作气体,利用低压等离子体增强化学气相沉积法制备了α-C∶H薄膜。利用傅里叶变换红外光谱仪和X射线光电子能谱对薄膜化学键和电子结构进行分析,并结合高斯分峰拟合分析了薄膜中sp3/sp2杂化键比值和sp3C杂化键分数。结果表明：薄膜中氢含量较高,主要以sp3C—H形式存在;工作气压越高,制备的薄膜中C=C键含量越少,薄膜中sp3/sp2杂化键比值和sp3C杂化键分数增加,薄膜稳定性提高。应用UV-VIS光谱仪,获得了波长在400~1 000 nm范围内薄膜的光吸收特性,结果显示: α-C∶H薄膜透过率可达98%。光学常数公式计算得到工作压强为4~14 Pa时光学带隙在2.66~2.76之间,并均随着工作气压的升高而增大。结果表明,随工作气压的升高,薄膜内sp3键减小,从而促使透过率、光学带隙增大。