Atomgewichte

Analytical and Bioanalytical Chemistry -     

Indentation of poly(methyl methacrylate) under high‐pressure gases

The variation of the indentation hardness of a high molecular weight poly(methyl methacrylate) (PMMA) subjected to CO₂ and Ar at high pressure was measured in situ. The samples were subjected to gas exposure for 3 h at 40 °C before a conical indenter of an included angle at 105 °, with a fixed load of 0.237 kg, was applied for a loading time of 60 s. The data show that both CO₂ and Ar reduce the hardness of PMMA to a comparable extent at low pressures. The hardness of PMMA subjected to Ar indicates a minimum at about 4 MPa and then increases. CO₂ produced a monotone decreasing trend in hardness in the pressure range studied, and the glass‐transition temperature (T_g) was achieved at about 6.0 MPa. The change in hardness is attributed to plasticization of the polymer matrix that is more extensive for CO₂. The relationship between the change in hardness for this PMMA subjected to high‐pressure CO₂, the corresponding change in the T_g, and the associated swelling of the polymer is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3020–3028, 2001     

Jamming III: Characterizing randomness via the entropy of jammed matter

The nature of randomness in disordered packings of frictional and frictionless spheres is investigated using theory and simulations of identical spherical grains. The entropy of the packings is defined through the force and volume ensemble of jammed matter and this is shown to be difficult to calculate analytically. A mesoscopic ensemble of isostatic states is then utilized in an effort to predict the entropy through the definition of a volume function that is dependent on the coordination number. Equations of state are obtained relating entropy, volume fraction and compactivity characterizing the different states of jammed matter, and elucidating the phase diagram for jammed granular matter. Analytical calculations are compared to numerical simulations using volume fluctuation analysis and graph theoretical methods, with reasonable agreement. The entropy of the jammed system reveals that random loose packings are more disordered than random close packings, allowing for an unambiguous interpretation of both limits. Ensemble calculations show that the entropy vanishes at random close packing (RCP), while numerical simulations show that a finite entropy remains in the microscopic states at RCP. The notion of a negative compactivity, which explores states with volume fractions below those achievable by existing simulation protocols, is also explored, expanding the equations of state. The mesoscopic theory reproduces the simulations results in shape well, though a difference in magnitude implies that the entire entropy of the packing may not be captured by the methods presented herein. We discuss possible extensions to the present mesoscopic approach describing packings from random loose packing (RLP) to RCP to the ordered branch of the equation of state in an effort to understand the entropy of jammed matter in the full range of densities from RLP to face-centered cubic (FCC) packing.     

Search for Theta++ pentaquarks in the exclusive reaction gammap-->K+K-p

The reaction gammap --> pK+K- was studied at Jefferson Lab with photon energies from 1.8 to 3.8 GeV using a tagged photon beam. The goal was to search for a Theta++ pentaquark, a narrow, doubly charged baryon state having strangeness S=+1 and isospin I=1, in the pK+ invariant mass spectrum. No statistically significant evidence of a Theta++ was found. Upper limits on the total and differential cross section for the reaction gammap --> K-Theta++ were obtained in the mass range from 1.5 to 2.0 GeV/c2, with an upper limit for a narrow resonance with a mass M(Theta++) = 1.54 GeV/c2 of about 0.15 nb, 95% C.L.. This result places a stringent upper limit on the Theta++ width Gamma(Theta++) <0.1 MeV/c2.     

Entropy of jammed matter

We investigate the nature of randomness in disordered packings of frictional spheres. We calculate the entropy of 3D packings through the force and volume ensemble of jammed matter, a mesoscopic ensemble and numerical simulations using volume fluctuation analysis and graph theoretical methods. Equations of state are obtained relating entropy, volume fraction and compactivity characterizing the different states of jammed matter. At the mesoscopic level the entropy vanishes at random close packing, while the microscopic states contribute to a finite entropy. The entropy of the jammed system reveals that the random loose packings are more disordered than random close packings, allowing for an unambiguous interpretation of both limits.     

Characterization of the third-harmonic radiation generated by intense laser self-formed filaments propagating in air

We perform laboratory experiments to study ultraviolet radiation generated by intense self-formed laser filaments produced by propagating high-power femtosecond laser pulses in air. The laser used in the experiment is a 0.5 TW Ti:sapphire system with the center wavelength at 800 nm. The observed ultraviolet emission occurs in the form of the third harmonic and frequency-upshifted radiation from the fundamental. We present direct characterization of the generated harmonic and frequency-upshifted radiation, including transverse imaging and spatially resolved spectral measurements.     

Photo‐enhanced catalytic activity of spray‐coated Cu2SnSe3 nanoparticle counter electrode for dye‐sensitised solar cells

Cu₂SnSe₃ nanoparticles are synthesised using oleylamine as both a solvent and capping agent and spray coated to form dye‐sensitised solar cell (DSSC) counter electrodes (CEs) using earth‐abundant elements. The film requires annealing at only 400 °C in nitrogen, which is a lower temperature than previous reports of both Cu₂SnSe₃and Cu₂ZnSnSe₄ films, also avoiding the use of Se gas. The composition and phase of the material is confirmed to be kesterite Cu₂SnSe₃. DSSCs using Cu₂SnSe₃ CEs give a power conversion efficiency of 4.87%, compared to 5.35% when using Pt. Electrochemical impedance spectroscopy indicates that the performance of the Cu₂SnSe₃ CE is enhanced under illumination, leading to a drop in the charge transfer resistance. This illumination‐induced enhancement of the catalytic activity provides a novel mechanism for the enhancement of CE performance in DSSCs.