Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

Evaluation of Charged Defect Energy in Two-Dimensional Semiconductors for Nanoelectronics: The WLZ Extrapolation Method

Defects play a central role in controlling the electronic properties of two-dimensional (2D) materials and realizing the industrialization of 2D electronics. However, the evaluation of charged defects in 2D materials within first-principles calculation is very challenging and has triggered a recent development of the WLZ (Wang, Li, Zhang) extrapolation method. This method lays the foundation of the theoretical evaluation of energies of charged defects in 2D materials within the first-principles framework. Herein, the vital role of defects for advancing 2D electronics is discussed, followed by an introduction of the fundamentals of the WLZ extrapolation method. The ionization energies (IEs) obtained by this method for defects in various 2D semiconductors are then reviewed and summarized. Finally, the unique defect physics in 2D dimensions including the dielectric environment effects, defect ionization process, and carrier transport mechanism captured with the WLZ extrapolation method are presented. As an efficient and reasonable evaluation of charged defects in 2D materials for nanoelectronics and other emerging applications, this work can be of benefit to the community.     

Analysis on X-Ray Laser Generation with EM-Wave Wiggler

The possibility of realizing SASE Free Election Laser in x-ray waveband with EM-wave wiggler is studied in this paper. SASE effect including saturation length, saturation power and nonlinear process is explored through a 3-D simulation code. A utilization of seed light from laser plasma x-ray is also analyzed, which demonstrates the feature of shortening the interaction length for saturation. The results show that sizeable output power of x-ray laser would be generated with a middle energy electron beam.     

Extrusion of pastes with a piston extruder for the determination of the local solid and fluid concentration, the local porosity and saturation and displacement profiles by means of NMR imaging

 Nuclear Magnetic Resonance (NMR) was used to investigate the extrusion behaviour of PTFE pastes in a ram extruder. By means of ¹H-NMR imaging (MRI) it is possible to determine the local proton density and therefore, the local fluid concentration. The ¹⁹F-MRI provides the local solid concentration. Thus the local saturation and the local porosity can be calculated with the information of the local fluid and solid concentration. Furthermore displacement profiles can be derived from NMR images by means of correlation techniques without any preparation or marking of the pastes. Received: 8 May 2000   Accepted: 1 May 2001     

An investigation on planar dielectric light collectors for illumination and solar energy applications

In this paper the performances of inhomogeneous dielectric slabs as solar light collectors for both illumination and solar energy applications are analysed.     

Enhancing the Bolzon–Schrefler–Zienkiewicz Constitutive Model for Partially Saturated Soil

This paper presents an enhanced version of the elasto-plastic model for partially saturated soil first proposed by Bolzon, Schrefler and Zienkiewicz in 1996, “BSZ” model, which uses the effective stress tensor and suction as independent stress variables. It is recalled that the effective stress tensor proposed by Lewis and Schrefler in 1982 is thermodynamically consistent and, compared with other choices of stress tensors, results particularly suitable for partially saturated soil mechanics. A hydraulic constitutive relationship and a hydraulic hysteresis are introduced in the model, to take into account the irreversible deformation during cyclic drying and wetting until structural collapse. For this reason the plastic rate of strain is split into the sum of two components: one depending on the effective stress tensor and the other one on suction. This is the new feature of the BSZ model. This enhanced model is then cast into a thermodynamical framework at macroscopic level and it is shown that it is possible to derive the constitutive law from the Helmholtz free energy and a dissipation function, both for associative and non- associative plasticity. Finally the model predictions have been compared with experimental data for Sion slime, with particular emphasis on the deviatoric part, and model predictions of hysteretic behaviour have been investigated in case of a wetting and drying cycle on compacted betonite–kaolin.     

Group Representation of Relativistic Quantum Crystal Optics

A group representation of radiation propagation in an anisotropic medium is developed. The system of wave equations for electromagnetic potentials, obtained from the Maxwell equations with account for the constitutive equations, has been factorized. It is shown that the linear differential operator of the factorized system is orthogonal in transparent crystals and unitary in gyrotropic ones and is represented through the momentum operator. On the basis of the commutation relations for the components of this operator, the eigenvalue problem has been solved and the expression for the change in the radiant energy in the crystal in the form of spherical waves has been obtained. The dependences of the ray and phase velocities and the polarization vectors of waves on the birefringence anisotropy and gyrotropy as well as on the angular momentum, displacement current, and bound charge determining them have been analyzed. It has been established that in the general case of gyrotropic crystals where the nonreciprocity phenomenon takes place and in magnetoelectrics Maxwell equations are represented in a form similar to the Dirac equations and the electromagnetic radiation is correctly described by means of bispinors and is quantized as fermions.     

Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐hexafluoropropane

To investigate the position and amount of the CF₃ group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF₃ groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF₃ group close to the imide group was more effective in lowering the color; this means that CF₃ of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF₃ groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003     

Novel,organosoluble, light‐colored fluorinated polyimides based on 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl or 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl

Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004     

Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004