Modeling and simulation of first and second sound in solids

We investigate the propagation of mechanical and thermal waves in solids at cryogenic temperatures. The latter are known as the second sound phenomenon. It occurs, e.g., in dielectric solids and differs greatly from the classical case in which the heat transport proceeds by diffusion. Since Fourier’s law of heat conduction fails for modeling second sound, we apply a non-classical one. During the last two decades, the non-classical thermoelastodynamic theory of Green and Naghdi enjoys steadily growing research activities.     

Preparation and some properties of a polyethyleneimine-agarose metal adsorbent

An adsorbent for metal ions has been prepared by reacting high molecular weight polyethyleneimine (PEI) with a crosslinked and activated agarose gel, Novarose. The synthesis variables, i.e. time, temperature, pH, PEI concentration and PEI/Novarose ratio, were optimized in order to obtain a high metal binding capacity of the adsorbent. The binding capacity for Cu(2+) is 500 micromol/ml packed adsorbent. A number of properties of the adsorbent relevant for metal ion accumulation has been investigated for Cu(2+), Ni(2+), Cd(2+) and Zn(2+). Adsorption capacities, adsorption isotherms, distribution coefficients, recoveries and relative rates of accumulation were determined. The adsorbent can be used for preconcentration and for separation of interfering alkali and alkaline earth metals in analytical applications.     

Tribochemische und thermische Umwandlungen von LnTa3O9 (Ln = Pr,Nd) – röntgenographische und elektronenmikroskopische Untersuchungen

Tribochemical and Thermal Transitions of LnTa₃O₉ (Ln = Pr, Nd) — X-ray and Electron Microscopic Investigations Upon grinding crystals of M1? LnTa₃O₉ (Ln = Pr, Nd) [3] undergo a tribochemical phase transition. This leads to a new modifikation M2? LnTa₃O₉ with a significant higher density. We tried to find out more about the structure with high resolution electron microscopic investigations. According to electron diffraction and powder patterns the lattice parameters are (CuKα₁, λ = 1,54051 Å): M2? PrTa₃O₉: a = 6.2545(7) Å, b = 7.6736(7) Å, c = 6.5316(8) Å, β = 93.93(9)°; M2? NdTa₃O₉: a = 6.2552(5) Å, b = 7.6598(7) Å, c = 6.5103(4) Å, β = 94.096(7)°; (Z = 2). Using the intensities of powder patterns two structure models were calculated (space group P2₁/m, P2/m; R < 20%, heavy metal positions only). A through focus series of high resolution images was in better agreement with the first model (space group P2₁/m). Both models show a remarkable similarity to the structure of M? CeTa₃O₉ [4]. A thermal phase transition leads to M? PrTa₃O₉ and M? NdTa₃O₉ which are both isostructural to M? CeTa₃O₉.     

Melt spinning of propylene carbonate‐plasticized poly(acrylonitrile)‐co‐poly(methyl acrylate)

The primary use of poly(acrylonitrile) (PAN) fibers, commonly referred to as acrylic fibers, is in textile applications like clothing, furniture, carpets, and awnings. All commercially available PAN fibers are processed by solution spinning; however, alternative, more cost‐effective processes like melt spinning are still highly desired. Here, the melt spinning of PAN‐co‐poly(methyl acrylate) (PMA) plasticized with propylene carbonate (PC) at 175°C is reported. The use of methyl acrylate (MA) as comonomer and PC as an external plasticizer renders the approach a combination of internal and external plasticization. Various mixtures of PAN and PC used in this work were examined by rheology, subjected to melt spinning, followed by discontinuous and continuous washing, respectively. The best fibers were derived from a PAN‐co‐PMA copolymer containing 8.1 mol‐% of MA having a number‐average molecular weight M _n of 34 000 g/mol, spun in the presence of 22.5 wt.‐% of PC. The resulting fibers were analyzed by scanning electron microscopy and wide‐angle X‐ray scattering (WAXS), and were subjected to mechanical testing.     

Site‐Selective Oxidation of Monolayered Liquid‐Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile

In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS₂ with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS₂ is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.     

Experimental and Computational Studies of Anti‐Bredt Amidinium Salts

Experimental and computational investigations of anti‐Bredt amidinium salts are presented. Calculations show that the pyramidalization of an amino group can significantly destabilize the formal carbocation center of amidiniums, due to the decreased π donation. In some cases, the unfavorable ‐I effect of nitrogen surpasses its beneficial +M effect, and amidiniums become less stable than iminiums. It is shown that although 1‐aza‐3‐azonia[3.3.1]bicyclo‐non‐2‐enes can be isolated, they feature a nonclassical reactivity, which is more typical for iminium than amidinium salts, such as pronounced electrophilicity and azomethineylide instead of carbene formation.