Einfluß von Topologie und Verscherung auf Dynamik und mechanische Parameter bei Homopolymeren

Die FT-Rheologie wird zur Unterscheidung verschiedener Kamm-Topologien in Polystyrollösungen und –schmelzen angewendet. Die Polystyrole werden in Abhängigkeit der Deborahzahl De unter LAOS-Bedingungen vermessen. Die Meßergebnisse zeigen, daß der Schritt von wohldefinierten Systemen (lineare Ketten, Sterne) zu solchen mit statistischer Verteilung wie in Kämmen zu großen Veränderungen sowohl im linearen als auch im nichtlinearen Bereich der rheologischen Messungen führt. Sowohl die Masterkurven als auch die Intenstiäten I3/1 und Phasen Phi3 der Nichtlinearitäten der einzelnen Proben weisen jeweils deutliche Unterschiede untereinander auf. Diese sind durch die bisherigen Ergebnisse noch nicht vollständig mit topologischen Merkmalen in Verbindung zu bringen. Die Messungen wurden mit dem von McLeish eingeführten Pom-pom Modell und daraus weiterentwickelten double convected-Pom-pom Modell (DCPP) simuliert und lieferten gute Übereinstimmung sowie auch Vorhersagen über den experimentell nicht mehr zugänglichen Bereich. Zur Untersuchung des Einflusses von mechanischer Scherung auf die lokale, molekulare Dynamik wird das LAOS-Experiment in situ mit dielektrischer Spektroskopie kombiniert. Dazu wurde eine Apparatur entwickelt, die das hochsensitive ARES-Rheometer mit dem hochauflösenden dielektrischen ALPHA-Analyzer verbindet. Mit dieser Apparatur wurde das Typ-A Polymer 1,4-cis-Polyisopren, mit einem Dipolmoment entlang des Rückgrats, bei oszillatorischer Scherung unter gleichzeitiger Aufnahme eines dielektrischen Spektrums vermessen. Es konnte gezeigt werden, daß die oszillatorische Verscherung weder die charakteristische Relaxationszeit noch die Form des Normal Mode Peaks beeinflußt, wohl aber die dielektrische Stärke Delta epsilon. Diese entspricht der Fläche unter dem e“-Peak und kann mit einer Debye- und einer Cole/Davidson-Funktion angepasst werden. Die Abnahme der dielektrischen Stärke mit zunehmender Scheramplitude kann mit der Orientierungsverteilung der End-zu-End-Vektoren in der Probe erklärt werden.

Rheology and Fourier-transform rheology on water-based systems

The influence of shear fields on water-based systems was investigated within this thesis. The non-linear rheological behaviour of spherical and rod-like particles was examined with Fourier-Transform rheology under LAOS conditions. As a model system for spherical particles two different kinds of polystyrene dispersions, with a solid content higher than 0.3 each, were synthesised within this work. Due to the differences in polydispersity and Debye-length, differences were also found in the rheology. In the FT-rheology both kinds of dispersions showed a similar rise in the intensities of the magnitudes of the odd higher harmonics, which were predicted by a model. The in some cases additionally appearing second harmonics were not predicted. A novel method to analyse the time domain signal was developed, that splits the time domain signal up in four characteristic functions. Those characteristic functions correspond to rheological phenomena. In some cases the intensities of the Fourier components can interfere negatively. FD-virus particles were used as a rod-like model system, which already shows a highly non-linear behaviour at concentrations below 1. % wt. Predictions for the dependence of the higher harmonics from the strain amplitude described the non-linear behaviour well at large, but no so good at small strain amplitudes. Additionally the trends of the rheological behaviour could be described by a theory for rod-like particles. An existing rheo-optical set-up was enhanced by reducing the background birefringence by a factor of 20 and by increasing the time resolution by a factor of 24. Additionally a combination of FT-rheology and rheo-optics was achieved. The influence of a constant shear field on the crystallisation process of zinc oxide in the presence of a polymer was examined. The crystallites showed a reduction in length by a factor of 2. The directed addition of polymers in combination with a defined shear field can be an easy way for a defined change of the form of crystallites.

Prehistoric hand stencils at Fern Cave, North Queensland (Australia): environmental and chronological implications of Raman spectroscopy and FT-IR imaging results

Raman spectroscopy and FT-IR imaging analyses of cave wall pigment samples from north Queensland (Australia) indicate that some hand stencils were undertaken during a dry environmental phase indicating late Holocene age. Other, earlier painting episodes also took place during dry environmental periods of the terminal Pleistocene and/or early Holocene. These results represent a rare opportunity to attain chronological information for rock art in conditions where insufficient carbon is present for radiocarbon dating.

FT Raman spectroscopic characterization of oxalate precursors to YBCO superconductors

FT Raman spectroscopy has been used to characterise the composition of the oxalate precursor to YBCO superconductors. By comparison to spectra of barium, copper and yttrium oxalate it is concluded that the co-precipitate incorporates not only the individual oxalate species but also a species ascribed to a mixed oxalate system. Significantly, Raman spectroscopy demonstrated that the precursor was not amorphous as previously deduced from XRD studies. In contrast, it is hypothesised that the sample consists of very small crystalline particles.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism

Homologs of FT, CEN and FD respond to developmental and environmental signals affecting growth and flowering in the perennial vine kiwifruit

FLOWERING LOCUS T (FT) and CENTRORADIALIS (CEN) homologs have been implicated in regulation of growth, determinacy and flowering. The roles of kiwifruit FT and CEN were explored using a combination of expression analysis, protein interactions, response to temperature in high-chill and low-chill kiwifruit cultivars and ectopic expression in Arabidopsis and Actinidia. The expression and activity of FT was opposite from that of CEN and incorporated an interaction with a FLOWERING LOCUS D (FD)-like bZIP transcription factor. Accumulation of FT transcript was associated with plant maturity and particular stages of leaf, flower and fruit development, but could be detected irrespective of the flowering process and failed to induce precocious flowering in transgenic kiwifruit. Instead, transgenic plants demonstrated reduced growth and survival rate. Accumulation of FT transcript was detected in dormant buds and stem in response to winter chilling. In contrast, FD in buds was reduced by exposure to cold. CEN transcript accumulated in developing latent buds, but declined before the onset of dormancy and delayed flowering when ectopically expressed in kiwifruit. Our results suggest roles for FT, CEN and FD in integration of developmental and environmental cues that affect dormancy, budbreak and flowering in kiwifruit.

Non-destructive prediction of 'Hass' avocado dry matter via FT-NIR spectroscopy.

BACKGROUND: The inability to consistently guarantee internal quality of horticulture produce is of major importance to the primary producer, marketers and ultimately the consumer. Currently, commercial avocado maturity estimation is based on the destructive assessment of percentage dry matter (%DM), and sometimes percentage oil, both of which are highly correlated with maturity. In this study the utility of Fourier transform (FT) near-infrared spectroscopy (NIRS) was investigated for the first time as a non-invasive technique for estimating %DM of whole intact 'Hass' avocado fruit. Partial least squares regression models were developed from the diffuse reflectance spectra to predict %DM, taking into account effects of intra-seasonal variation and orchard conditions. RESULTS: It was found that combining three harvests (early, mid and late) from a single farm in the major production district of central Queensland yielded a predictive model for %DM with a coefficient of determination for the validation set of 0.76 and a root mean square error of prediction of 1.53% for DM in the range 19.4-34.2%. CONCLUSION: The results of the study indicate the potential of FT-NIRS in diffuse reflectance mode to non-invasively predict %DM of whole 'Hass' avocado fruit. When the FT-NIRS system was assessed on whole avocados, the results compared favourably against data from other NIRS systems identified in the literature that have been used in research applications on avocados.

Effects of seasonal variability on FT-NIR prediction of dry matter content for whole Hass avocado fruit

Fourier Transform (FT)-near infra-red spectroscopy (NIRS) was investigated as a non-invasive technique for estimating percentage (%) dry matter of whole intact 'Hass' avocado fruit. Partial least squares (PLS) calibration models were developed from the diffuse reflectance spectra to predict % dry matter, taking into account effects of seasonal variation. It is found that seasonal variability has a significant effect on model predictive performance for dry matter in avocados. The robustness of the calibration model, which in general limits the application for the technique, was found to increase across years (seasons) when more seasonal variability was included in the calibration set. The R-v(2) and RMSEP for the single season prediction models predicting on an independent season ranged from 0.09 to 0.61 and 2.63 to 5.00, respectively, while for the two season models predicting on the third independent season, they ranged from 0.34 to 0.79 and 2.18 to 2.50, respectively. The bias for single season models predicting an independent season was as high as 4.429 but <= 1.417 for the two season combined models. The calibration model encompassing fruit from three consecutive years yielded predictive statistics of R-v(2) = 0.89, RMSEP = 1.43% dry matter with a bias of -0.021 in the range 16.1-39.7% dry matter for the validation population encompassing independent fruit from the three consecutive years. Relevant spectral information for all calibration models was obtained primarily from oil, carbohydrate and water absorbance bands clustered in the 890-980, 1005-1050, 1330-1380 and 1700-1790 nm regions. These results indicate the potential of FT-NIRS, in diffuse reflectance mode, to non-invasively predict the % dry matter of whole 'Hass' avocado fruit and the importance of the development of a calibration model that incorporates seasonal variation. Crown Copyright (c) 2012 Published by Elsevier B.V. All rights reserved.

A novel method for the age estimation of Saddletail snapper (Lutjanus malabaricus) using Fourier Transform-near infrared (FT-NIR) spectroscopy

Near infrared (NIR) spectroscopy was investigated as a potential rapid method of estimating fish age from whole otoliths of Saddletail snapper (Lutjanus malabaricus). Whole otoliths from 209 Saddletail snapper were extracted and the NIR spectral characteristics were acquired over a spectral range of 800–2780 nm. Partial least-squares models (PLS) were developed from the diffuse reflectance spectra and reference-validated age estimates (based on traditional sectioned otolith increments) to predict age for independent otolith samples. Predictive models developed for a specific season and geographical location performed poorly against a different season and geographical location. However, overall PLS regression statistics for predicting a combined population incorporating both geographic location and season variables were: coefficient of determination (R2) = 0.94, root mean square error of prediction (RMSEP) = 1.54 for age estimation, indicating that Saddletail age could be predicted within 1.5 increment counts. This level of accuracy suggests the method warrants further development for Saddletail snapper and may have potential for other fish species. A rapid method of fish age estimation could have the potential to reduce greatly both costs of time and materials in the assessment and management of commercial fisheries.