Thermodiffusion of polymer solutions and colloidal dispersions in mixed solvents.

Two-color optical measurements of thermodiffusion in ternary mixtures frequently suffer from ill-conditioned contrast factor matrices, whose inversion leads to very large experimental errors. In this contribution, we show how the error amplification can be avoided in situations where a priori knowledge about the directions of the eigenvectors of the diffusion matrix is available. We present optical beam deflection experiments on solutions of the polymer polystyrene of Mw = 4880 g/mol in a mixed solvent of toluene and cyclohexane. In this system, the two diffusion eigenvalues differ by almost one order of magnitude. The large eigenvalue can be attributed to the interdiffusion of the two solvents and the small one to the polymer diffusion relative to the mixed solvent. The pre-selection of the eigenvectors renders the method stable against fluctuations of the experimental parameters. Both the diffusion and the Soret coefficients attributed to the two modes agree very well with the respective values of corresponding binary mixtures.

The Soret coefficients of the ternary system water/ethanol/triethylene glycol and its corresponding binary mixtures.

Thermodiffusion in ternary mixtures is considered prototypic for the Soret effect of truly multicomponent systems. We discuss ground-based measurements of the Soret coefficient along the binary borders of the Gibbs triangle of the highly polar and hydrogen bonding ternary DCMIX3-system water/ethanol/triethylene glycol. All three Soret coefficients decay with increasing concentration, irrespective of the choice of the independent component, and show a characteristic sign change as a function of temperature and/or composition. With the exception of triethylene glycol/ethanol at high temperatures, the minority component always migrates toward the cold side. All three binaries exhibit temperature-independent fixed points of the Soret coefficient. The decay of the Soret coefficient with concentration can be related to negative excess volumes of mixing. The sign changes of the Soret coefficients of the binaries allow to draw far-reaching conclusions about the signs of the Soret coefficients of the corresponding ternary mixtures. In particular, we show that at least one ternary composition must exist, where all three Soret coefficients vanish simultaneously and no steady-state separation is observable.

The Soret effect in ternary mixtures of water+ethanol+triethylene glycol of equal mass fractions: Ground and microgravity experiments.

Measurements of the Soret and thermodiffusion coefficients of a symmetric ternary mixture with equal mass fractions of water, ethanol, and triethylene glycol have been performed by two-color optical beam deflection (2-OBD) and the thermogravitational column technique (TGC) in the laboratory and under microgravity conditions in the Selectable Optical Diagnostics Instrument (SODI) aboard the International Space Station. The results from all three experimental techniques agree within the experimental error bars, which result mainly from the inversion of the contrast factor matrices. TGC shows by far the lowest, 2-OBD the highest error amplification. The microgravity measurements are in between. The agreement with the microgravity results shows that thermosolutal convection could be well controlled in the 2-OBD experiments by a proper orientation of the temperature gradient. Despite the different condition numbers, the results are invariant under the choice of the independent compositions. Based on the orientation of the confidence ellipsoid in the ternary composition diagram, not all coefficients are equally affected by experimental errors. Although there are appreciable uncertainties for water and ethanol, the Soret and the thermodiffusion coefficients of triethylene glycol could be obtained with a good accuracy due to the favorable orientation of the confidence ellipsoid. We have found that water behaves thermophobic, corresponding to a positive Soret coefficient, whereas both ethanol and triethylene glycol are thermophilic with negative Soret coefficients. This resembles the behaviour of the binary system ethanol/water above the ethanol concentration of the sign change.

European Space Agency experiments on thermodiffusion of fluid mixtures in space.

This paper describes the European Space Agency (ESA) experiments devoted to study thermodiffusion of fluid mixtures in microgravity environment, where sedimentation and convection do not affect the mass flow induced by the Soret effect. First, the experiments performed on binary mixtures in the IVIDIL and GRADFLEX experiments are described. Then, further experiments on ternary mixtures and complex fluids performed in DCMIX and planned to be performed in the context of the NEUF-DIX project are presented. Finally, multi-component mixtures studied in the SCCO project are detailed.

Measurement of non-isothermal transport coefficients in a near-eutectic succinonitrile/(d)camphor mixture.

We have determined nonisothermal diffusive transport coefficients of a succinonitrile-(d)camphor mixture with a composition of c = 0.239 wt.-frac. (d)camphor at a temperature of 318.2 K, which is close to the eutectic point. The employed experimental techniques are optical beam deflection in a Soret cell and photon correlation spectroscopy. The diffusion coefficient is D = (1.43 ± 0.04) × 10-10 m2 s-1, the thermodiffusion coefficient is DT = (2.00 ± 0.06) × 10-12 m2 s-1 K-1, and the Soret coefficient is ST = (1.40 ± 0.02) × 10-2 K-1. Camphor migrates toward the lower and succinonitrile migrates toward the higher temperatures. While the diffusion coefficient is in good agreement with the literature, the Soret coefficient has been determined for the first time. Our analysis shows that a significant concentration shift can be established in the liquid mixture in the presence of a temperature gradient. The mixture has a negative separation ratio, which leads to convective instabilities if heated from above.

Ultrasensitive quartz crystal microbalance sensors for detection of M13-Phages in liquids.

Quartz crystal microbalance (QCM) sensors are widely used for determining liquid properties or probing interfacial processes. For some applications the sensitivity of the QCM sensors typically used (5-20 MHz) is limited compared with other biosensor methods. In this study ultrasensitive QCM sensors with resonant frequencies from 39 to 110 MHz for measurements in the liquid phase are presented. The fundamental sensor effect of a QCM is the decrease of the resonant frequency of an oscillating quartz crystal due to the binding of mass on a coated surface during the measurement. The sensitivity of QCM sensors increases strongly with an increasing resonant frequency and, therefore, with a decreasing thickness of the sensitive area. The new kind of ultrasensitive QCM sensors used in this study is based on chemically milled shear mode quartz crystals which are etched only in the center of the blank, forming a thin quartz membrane with a thick, mechanically stable outer ring. An immunoassay using a virus specific monoclonal antibody and a M13-Phage showed an increase in the signal to noise ratio by a factor of more than 6 for 56 MHz quartz crystals compared with standard 19 MHz quartz crystals, the detection limit was improved by a factor of 200. Probing of acoustic properties of glycerol/water mixtures resulted in an increase in sensitivity, which is in very good agreement with theory. Chemically milled QCM sensors strongly improve the sensitivity in biosensing and probing of acoustic properties and, therefore, offer interesting new application fields for QCM sensors.

Multicentre evaluation of a new point-of-care test for the quantitative determination of D-dimer.

Imprecision studies, interference testing and multicentre method comparisons using patient samples were carried out with of a new point-of-care test for D-dimer (CARDIAC D-Dimer). The CV of the within-series and the day-to-day imprecision with blood samples and control materials were between 7% and 13%. Compared with Tina-quant D-Dimer, CARDIAC D-Dimer showed a good correlation and accuracy (n=353; r=0.91; y=1.06x-0.03), compared with STA LIATEST D-Dimer some poorer accuracy (n=304; r=0.91; y=1.12x-0.03). No interference was detected for different hematocrit values (16% to 51%) and in investigations with hemoglobin (up to 0.13 mmol/l), biotin (up to 30 microg/l), bilirubin (up to 340 micromol/l), intralipid (up to 31.1 mmol/l) and rheumatic factor (up to 79 IU/ml). Overdosing or underdosing by 10 microl did not affect the test result. The diagnostic sensitivity of CARDIAC D-Dimer for the detection of acute venous thromboembolic diseases was 100% in our study. With CARDIAC D-Dimer reliable quantitative D-dimer results can be easily obtained. Because of the good analytical and clinical agreement with Tina-quant D-Dimer, it should be suitable for ruling out venous thromboembolic diseases.