Viscosity Measurements of Three Base Oils and One Fully Formulated Lubricant and New Viscosity Correlations for the Calibration Liquid Squalane.

The viscosities of three pentaerythritol tetraalkanoate ester base oils and one fully formulated lubricant were measured with an oscillating piston viscometer in the overall temperature range from 275 K to 450 K with pressures up to 137 MPa. The alkanoates were pentanoate, heptanoate, and nonanoate. Three sensing cylinders covering the combined viscosity range from 1 mPa·s to 100 mPa·s were calibrated with squalane. This required a re-correlation of a squalane viscosity data set in the literature that was measured with a vibrating wire viscometer, with an estimated extended uncertainty of 2 %, because the squalane viscosity formulations in the literature did not represent this data set within its experimental uncertainty. In addition, a new formulation for the viscosity of squalane at atmospheric pressure was developed that represents experimental data from 169.5 K to 473 K within their estimated uncertainty over a viscosity range of more than eleven orders of magnitude. The viscosity of squalane was measured over the entire viscometer range, and the results were used together with the squalane correlations to develop accurate calibrating functions for the instrument. The throughput of the instrument was tripled by a custom-developed LabVIEW application. The measured viscosity data for the ester base oils and the fully formulated lubricant were tabulated and compared with literature data. An unpublished viscosity data set for pentaerythritol tetrapentanoate measured in this laboratory in 2006 at atmospheric pressure from 253 K to 373 K agrees with the new data within their experimental uncertainty and confirms the deviations from the literature data. The density data measured in this project for the three base oils deviate from the literature data in a way that is by sign and magnitude consistent with the deviations of the viscosity data. This points to differences in the sample compositions as the most likely cause for the deviations.

Compressed-liquid Densities of the Binary Mixture Dimethyl Carbonate + Heptane at Three Compositions.

Compressed-liquid densities of the binary system dimethyl carbonate + heptane have been measured with a vibrating-tube densimeter over the temperature and pressure ranges of 270 K to 470 K, and 1 MPa to 50 MPa at three compositions of the mixture. The measurements are part of an effort to better understand the molecular interactions of polar/non-polar mixtures. These types of mixtures often exhibit very non-ideal behavior. By measuring the mixture at three compositions and over a large range of temperature and pressure, the non-ideality can be assessed. There are no high-pressure liquid density data for this binary system in the literature, thus data reported here could only be compared to literature data at atmospheric pressure to establish their quality. The majority of literature data agree well with the presented results which have a maximum expanded uncertainty of 1.63 kg·m-3 (for the composition with the greatest mole fraction of dimethyl carbonate). The non-ideality for the mixture, in the temperature, pressure and composition range of this study was found to be minimal. This is rationalized by considering the molecular sizes, shapes, and charge distributions of the pure components and the attractive parts of their intermolecular force fields as they are reflected in the temperature ranges of their vapor pressure curves.

Wide-ranging Absolute Viscosity Measurements of Sub- and Supercritical 1,1,1-trifluoroethane (R143a).

The viscosity of 1,1,1-trifluoroethane (R143a) was measured with a piezoelectrically actuated, torsionally vibrating quartz sensor. The measurements extended over a temperature range from 300 K to 440 K with pressures to 68 MPa and covered states from the dilute gas to the compressed liquid. The influence of the drive voltage on the torsional displacement of the vibrator in fluid and in vacuum was systematically investigated. Since R143a is highly polar, the sample conductance and susceptance were also monitored with the sensor to detect possible electroviscous contributions in the measured viscosities. None were identified so that the estimated uncertainty of the measurements remains at 2 % at a 95 % confidence level (coverage factor k = 2). The results agree well within this margin with literature data that were determined with four other viscometric techniques.

Reference Correlation for the Viscosity of Carbon Dioxide.

A comprehensive database of experimental and computed data for the viscosity of carbon dioxide (CO2) was compiled and a new reference correlation was developed. Literature results based on an ab initio potential energy surface were the foundation of the correlation of the viscosity in the limit of zero density in the temperature range from 100 K to 2000 K. Guided symbolic regression was employed to obtain a new functional form that extrapolates correctly to T → 0 K and to 10 000 K. Coordinated measurements at low density made it possible to implement the temperature dependence of the Rainwater-Friend theory in the linear-in-density viscosity term. The residual viscosity could be formulated with a scaling term ργ /T the significance of which was confirmed by symbolic regression. The final viscosity correlation covers temperatures from 100 K to 2000 K for gaseous CO2, and from 220 K to 700 K with pressures along the melting line up to 8000 MPa for compressed and supercritical liquid states. The data representation is more accurate than with the previous correlations, and the covered pressure and temperature range is significantly extended. The critical enhancement of the viscosity of CO2 is included in the new correlation.

Application of falling-needle rheometry to highly concentrated DNA solutions.

High-concentration DNA solutions are common both in vitro and in vivo, and understanding the rheological properties is a critical area of bioscience. Our previous measurements on high-concentration DNA solutions (2-6 mg/ml) interestingly provided evidence for a viscosity maximum with temperature. Under the influence of temperature, the measured viscosities indicated distinct differences in the interactions of highly polymerized DNA in unbuffered and buffered aqueous solutions. Under the same conditions, the buffered solutions were always less viscous, and in addition the viscosity maximum was not observed. In this research we have utilized a falling-needle rheometer in order to gain more insight into the nature of the previously observed viscosity maxima. The shape of the flow curves for all the DNA solutions indicated that the solutions are shear-thinning and has allowed us to confirm the existence of the viscosity maximum in unbuffered DNA solutions. Also we have been able to measure flow curves at very low shear rates, <10 s⁻¹. These results showed that the flow curves intersect and that the lower the concentration of DNA in solution, the lower is the temperature where the flow curves will intersect. Thus, the viscosity-temperature dependence is also a function of the shear rates experienced by the solution. Finally, as expected, the flow behavior of the DNA solutions becomes more Newtonian with increasing temperature, and there appears to be a small yield stress that decreases with increasing temperature.

Viscosity measurements of DNA solutions with and without condensing agents.

Aqueous solutions calf thymus DNA at three concentrations were studied by viscosity measurements at ambient pressure. A gravitational capillary viscometer and a rotating cylinder viscometer were employed. Three polycations were tested as viscosity-reducing agents with measurements from 25°C to 50°C. The most significant viscosity reduction was achieved with spermine in a solution of DNA at 2 mg/ml concentration. Measurements of DNA solutions without agents from 10°C to 90°C revealed concentration-dependent viscosity maxima in the range from 50°C to 65°C. The associated increases in viscosity were as high as 400%. A two-liquids model for solutions of double- and single-stranded DNA was developed that closely represented the experimental data.

Sealed Gravitational Capillary Viscometry of Dimethyl Ether and Two Next-Generation Alternative Refrigerants.

The viscosities of dimethyl ether (DME, C2H6O) and of the fluorinated propene isomers 2,3,3,3-tetrafluoroprop-1-ene (R1234yf, C3H2F4) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) were measured in a combined temperature range from 242 K to 350 K at saturated liquid conditions. The instrument was a sealed gravitational capillary viscometer developed at NIST for volatile liquids. Calibration and adjustment of the instrument constant were conducted with n-pentane. The repeatability of the measurements was found to be approximately 1.5 %, leading to a temperature-dependent estimated combined standard uncertainty of the experimental data between 5.7 % at 242 K for dimethyl ether and 2.6 % at 340 K for R1234yf. The measurements were supplemented by ab initio calculations of the molecular size, shape, and charge distributions of the measured compounds. The viscosity results for dimethyl ether were compared with literature data. One other data set measured with a sealed capillary viscometer and exceeding the present results by up to 7 % could be reconciled by applying the vapor buoyancy correction. Then, all data agreed within the estimated uncertainty of the present results. Viscosities for the fluorinated propene isomers deviate up to 4 % from values predicted with the NIST extended corresponding-states model. The viscosities of the two isomers do not scale with their dipole moments. While the measured viscosity of R1234ze(E) with the lower dipole moment is close to that of R134a, the refrigerant to be replaced, that of R1234yf with the higher dipole moment is up to 25 % lower. The viscosity of dimethyl ether is compared with those of water and methanol.

The effect of dissolved water on the viscosities of hydrophobic room-temperature ionic liquids.

Data for viscosity vs. water content for three hydrophobic room-temperature ionic liquids show that their viscosities are strongly dependent on the amount of dissolved water.

Transport coefficients of the Lennard-Jones model fluid. III. Bulk viscosity.

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This third of a series of four papers presents the results for the bulk viscosity. With comprehensive simulation data at over 350 state points, the temperature and density dependences of the bulk viscosity are characterized in this work over a wide range of fluid states. The bulk viscosity exhibits a large critical enhancement similar to that known for the thermal conductivity, but it extends much farther into the supercritical region and can be observed even at 4.5 times the critical temperature. An investigation of the pressure-fluctuation autocorrelation functions shows that the enhancement is caused by extremely slowly decaying pressure fluctuations.

Transport coefficients of the Lennard-Jones model fluid. II Self-diffusion.

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This second of a series of four papers presents the results for the self-diffusion coefficient, and discusses and interprets the behavior of this transport coefficient in the fluid region of the phase diagram. The uncertainty of the self-diffusion data is estimated to be 1% in the gas region and 0.5% at high-density liquid states. With the very accurate data, even fine details in the shape of the self-diffusion isotherms are resolved, and the previously little-investigated behavior of the self-diffusion coefficient at low-density gaseous states is analyzed in detail. Finally, aspects of the mass transport mechanisms on the molecular scale are explored by an analysis of the velocity autocorrelation functions.

Transport coefficients of the Lennard-Jones model fluid. I. Viscosity.

In an extensive computer simulation study, the transport coefficients of the Lennard-Jones model fluid were determined with high accuracy from equilibrium molecular-dynamics simulations. In the frame of time-correlation function theory, the generalized Einstein relations were employed to evaluate the transport coefficients. This first of a series of four papers presents the results for the viscosity, and discusses and interprets the behavior of this transport coefficient in the fluid region of the phase diagram. Moreover, the kinetic-kinetic, kinetic-potential, and potential-potential viscosity contributions are resolved over the whole range of fluid states, and their characteristic dependence on temperature and density is described. Finally, an additional analysis of the shear-stress correlation functions reveals aspects of the momentum-transport mechanisms on the molecular scale.

Through Measurement to Knowledge: The Inaugural Lecture of Heike Kamerlingh Onnes (1882).

This paper is a contribution to the NIST Centennial 2001. It presents the first complete English translation of the inaugural speech of Heike Kamerlingh Onnes on the occasion of his appointment as Professor at the University of Leiden (The Netherlands) in 1882. The speech is a snapshot of the scientific landscape of that time and lays out a vision. It advocates with enthusiasm the significance of quantitative measurements and the development of metrology standards. Although science and technology have advanced since then by orders of magnitude, a number of interesting parallels between then and now appear.