On the splitting of the CO 1π level in the chemisorption system CO/Ni(111): substrate or lateral interaction?

LCGTO Xα model cluster calculations have been carried out to rationalize the shape of the CO 1π band of the chemisorption system CO/Ni(111) observed in angular resolved photoemission. The splitting induced by substrate interaction at twofold bridging sites (0.4 eV) is much smaller than the value deduced from experiment (1.2 eV). From calculations on (CO) _n clusters lateral adsorbate interaction is estimated to cause a sizable broadening of the 1π band (1.2eV, in satisfactory agreement with experiment), but essentially no splitting (?0.1 eV). Therefore, rehybridisation due to local interaction does not seem to suffice as an explanation for the observed shape of the CO 1π band.     

About the fluorine chemistry in MCVD: The mechanism of fluorine incorporation into SiO2 layers

Fluorine incorporation during the deposition of silica layers is studied under MCVD conditions using C₂F₃Cl₃ as fluorine source. The experimental results are compared with known models of the incorporation mechanism. It is found that a gas/solid equilibrium during the consolidation step determines the final fluorine content of the layers.     

Frequency-dependent optical pumping in atomic ?-systems

We consider the effects of optical pumping on the conversion of laser-frequency modulation into intensity modulation by an atomic absorption line in a vapor of alkali atoms driven in a ?-configuration. It is found that, due to optical pumping in combination with the excited-state hyperfine structure, the absorption line shape is distorted substantially as the Fourier frequency of the FM is changed. The most significant effect of the distortion is a shift of the apparent line center, which depends on how the frequency of the modulation compares with the optical pumping rate. This shift has implications for locking lasers to atomic transitions and also for FM-AM noise conversion in atomic vapors.     

High-contrast coherent population trapping resonances using four-wave mixing in 87Rb

We demonstrate very high-contrast coherent population trapping(1) (CPT) resonances by using four-wave mixing in (87)Rb atoms. In the experiment, we take advantage of the spectral overlap between F=2-->F(?) and F=3-->F(?) optical resonances on the D1 line of (87)Rb and (85)Rb atoms, respectively, to eliminate the DC-light background from the CPT resonance signal. We observe a CPT resonance with a contrast in the range of 90%, compared with a few percent achieved by alternative methods.     

Slip flow of non-plasticized PVC compounds

Measurements on seven rigid PVC compounds were carried out with a slit rheometer working in combination with an injection moulding machine. Plastication of the compounds occurred in the screw of the plastication unit, which also forced the melt through the die with a controlled forward velocity. The rectangular slit had a length of 90 mm and a widthB of 20 mm. The heightH could be varied between 0.8 and 3.3 mm. Pressures and temperatures were recorded at several positions in and before the die. Measurements were carried out at shear rates from 10 to 2000 s^–1.When the reduced volume output was plotted against the wall shear stress _W , only four compounds showed master curves independent ofH, which is indicative of wall adhesion. In the other cases this plot did not produce such a master curve, but the plot of the mean velocity against _W was independent ofH (slip curve). This indicated that slip flow prevailed with a slip velocityv _G When, in the case of wall slip, the smooth inner surfaces of the die were replaced by surfaces with grooves perpendicular to the direction of flow, slip flow was prevented and the flow curves were shifted to much higher values of _Wc Above a critical value of the wall shear stress ( _Wc ) at which slip flow began, the output became nearly independent of _W . From the measurements made below _Wc a vs. relation for the shear flow could be derived, which was used to calculate the superimposed shear flow . Exact values of the slip velocity were then given by . Wall slip only occurred for compounds with a high shear viscosity, which corresponds to a high molecular weight (K-value).Dedicated to Professor H. Janeschitz-Kriegl on the occasion of his 60th birthday.     

Rheologische Messungen an Kunststoff-Schmelzen mit einem neuen Rotationsrheometer

Zusammenfassung In der vorliegenden Arbeit wird ein neues Rotationsrheometer vorgestellt und über Messungen an zwei Polymethylmethacrylat-Formmassen berichtet. Bei dem Rheometer handelt es sich um ein Couette-Rheometer mit feststehendem Innenzylinder als Meßkörper. Der Meßkörper ist beidseitig eingespannt. In dem geschlossenen Meßraum können die Schmelzen bis zu einem Druck von 500 bar belastet werden.Der zeitliche Verlauf der Schubspannung in den Schmelzen wird in Abhängigkeit von Temperatur und Druck aufgezeichnet.

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Summary A new type of rotational rheometer is described, and results for two samples of polymethylmethacrylate are reported. The rheometer consists of a Couette system with fixed inner cylinder, supported at both ends for torque measurements. Pressure may be varied up to 500 bar. Shear stresses have been recorded as a function of time, temperature and pressure.

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Nomenklatur C [kp cm^–2 s^–1] Steigung der Anlaufkurve im Nullpunkt - D [kp cm rad^–1] Direktionsmoment - E ₀ [kcal mol^–1] Aktivierungsenergie der Newtonschen Viskosität - G [kp cm^–2] Schubmodul - G [—] Griffith-Zahl - l [mm] Länge des Meßkörpers - p [kp cm^–2] Druck - R _i [mm] Radius des Innenzylinders - R _a [mm] Radius des Außenzylinders - t _max [s] Zeit, bei der das Maximum in der Anlaufkurve auftritt - T [°C] Temperatur - ₀ [cm² kp^–1] Druckkoeffizient der Newtonschen Viskosität - [s^–1] Schergeschwindigkeit - ₀ [kp s cm^–2] Newtonsche Viskosität - (g cm²] Trägheitsmoment des Meßkörpers - v ₀ [s^–1] Eigenfrequenz des Meßsystems - _max [kp cm^–2] maximale Schubspannung - _st [kp cm^–2] stationäre Schubspannung Mit 7 Abbildungen und 1 Tabelle