Thermophysical Properties of Binary and Ternary Fluid Mixtures from Dynamic Light Scattering

Several thermophysical properties of R507, a binary refrigerant mixture, and R404A, a ternary mixture, have been determined by dynamic light scattering (DLS), in both the liquid and the vapor states, along the saturation line approaching the vapor–liquid critical point. Data for the thermal diffusivitya and sound speed c _S cover a range of temperatures down to 270K, and data for the surface tension and kinematic viscosity down to 230K. For both mixtures the behavior of all properties determined can be correlated well by the mass-weighted sum of the respective pure component data, when all data are represented as a function of the reduced temperature.     

Optimization of Taylor Dispersion Technique for Measurement of Mutual Diffusion in Benchmark Mixtures

The Taylor dispersion technique has been used for measuring binary mutual diffusion coefficients for mixtures of 1,2,3,4-tetrahydronaphthalene (THN), isobutylbenzene (IBB) and dodecane (C₁₂ H ₂₆) at 0.5:0.5 mass fraction symmetric points, and for 0.9:0.1 mass fraction in IBB- C₁₂ H ₂₆. From the Stokes–Einstein equation and our experimental results, the limiting diffusion coefficients, D ⁰, and the equivalent solvated radii, R _s, have been estimated at infinitesimal concentration of these species (TNH, IBB and C₁₂ H ₂₆). The measured diffusion coefficients are used to estimate activity coefficients of the components in the mixture, contributing to a better understanding of the structure of such systems and of their thermodynamic behaviour at different concentrations. We have also investigated the diffusion properties for a ternary system containing equal mass fractions of all the components (0.33THN: 0.33IBB: 0.33C₁₂ H ₂₆) and at 298.15 K.     

动态光散射测量核壳双层纳米颗粒的研究

用动态光散射方法研究了以聚丙烯酸丁脂（PBA）为核、聚甲基丙烯酸甲脂（PMMA）为壳的核壳双层纳米颗粒的粒径和粒径分布。得出的结论为：由于同一粒径的单层介质颗粒和核壳双层纳米颗粒的散射光不同,在测量中若将核壳双层颗粒当作单层介质颗粒处理时,必将影响测量结果的表征。     

Thermophysical Properties of a Quaternary Refrigerant Mixture: Comparison of Dynamic Light Scattering Measurements with a Simple Prediction Method

Dynamic light scattering (DLS) has been used for the measurement of several thermophysical properties of a quaternary refrigerant mixture R-125/143a/32/134a in its liquid phase under saturation conditions. The thermal diffusivity and sound speed have been obtained by light scattering from bulk fluids over a temperature range from about 293 K up to the liquid–vapor critical point. By applying the method of DLS to a liquid–vapor interface, also called surface light scattering (SLS), the saturated liquid kinematic viscosity and surface tension can be determined simultaneously. These properties have been measured from about 243 to 343 K. The results are discussed in comparison with literature data and with a simple prediction method based on the mass-weighted properties of the pure components, expressed as functions of the reduced temperature. Once again, the simple prediction method was shown to be applicable for the calculation of different transport and other thermophysical properties of multicomponent refrigerant mixtures and this with sufficiently high accuracy for technical practice. Moreover, the input data for the simple prediction scheme can be reduced without loss of accuracy by treating binary or ternary mixtures as a subset of the multicomponent mixture.     

Infinite Dilution Binary Diffusion Coefficients of Benzene in Carbon Dioxide by the Taylor Dispersion Technique at Temperatures from 308.15 to 328.15 K and Pressures from 6 to 30 MPa

Infinite dilution binary diffusion coefficients, D₁₂, of benzene in carbon dioxide were measured by the Taylor dispersion technique at temperatures from 308.15 to 328.15 K and pressures from 6 to 30 MPa. The diffusion coefficients were obtained by the method of fitting in the time domain from the response curves measured with a UV–vis multidetector by scanning from 220 to 280 nm at increments of 1 or 4 nm. The wavelength dependences on the binary diffusion coefficient and the uncertainty were examined. The detector linearity, in terms of the relationship between the absorbance intensity and the product of the peak area of the response curve and CO₂ velocity, was found to fail at some characteristic absorption wavelengths such as 243, 248, 253, and 259 nm, even when the maximum absorbance intensities of the response curves were less than 0.5 and the fits were good. Although the D₁₂ values obtained from the response curves measured at 253 nm were almost consistent with some literature data, the D₁₂ values measured at wavelengths showing the detector linearity to be satisfactory, i.e., at 239 nm, were higher than those at 253 nm. The present D₁₂ data at 239 nm were well represented by the Schmidt number correlation, except for those showing the anomalous decrease in a plot of D₁₂ vs density in the density range from 250 to 500 kg·m^–3.     

Mie理论在静态光散射粒度测量的应用下限研究

测量下限是光散射颗粒测试技术的关键问题。本文通过理论分析、比较归一化散射光强的分布图和构造方差函数F(d)对颗粒散射光的光强分布进行了定性和定量的讨论,对Mie散射向Rayleigh散射趋近的情况进行了分析,讨论了散射光光强大小的分布,分析了测量不同粒径的颗粒的可行性,最终得到在入射光源是波长为0.6328μm的He-Ne激光器的情况下,当粒径d取200nm以上时,不同粒径颗粒的M ie散射光强分布有较大差别,适合用静态光散射的方法来判断颗粒粒径。     

Mutual Diffusion Coefficient and Dynamic Viscosity Near the Critical Consolute Point Probed by Dynamic Light Scattering

The possibility of applying dynamic light scattering to simultaneous determination of the mutual diffusion coefficient and the viscosity of binary liquid systems was studied near the critical consolute point. When seed particles are added to the system, the particle diffusion coefficient is measured, and the viscosity is obtained using the Stokes–Einstein relation. Since the amplitude of light scattered from concentration fluctuations is low in a mixture with a small difference between the refractive indices of the pure components, this approach allowed the determination of the viscosity of a critical mixture of nitroethane and isooctane, without a signal component from mutual diffusivity superimposed. In contrast, particle aggregation prevented the determination of the viscosity of a critical mixture of triethylamine and water. Despite this difficulty, and an unidentified contribution in the signals obtained, the mutual diffusion coefficient and the critical exponent v could be determined in this system without a noticeable influence from the addition of seed particles.     

Characterization of Macromolecular Solutions by a Combined Static and Dynamic Light Scattering Technique

The combination of quasi-elastic light scattering (LS) with integrated scattered intensity measurements in the same sample has been applied to study polymer and polymer–protein aqueous solutions. The molecular weight, the radius of gyration, and the second virial coefficient for thermosensitive polymer [poly(N-isopropylacrylamid)] solutions before and after precipitation transition have been obtained using Zimm plot calculations. The precipitation curve (intensity versus temperature dependence) for polymer solutions has been experimentally obtained using the light scattering setup. For the first time the static and dynamic LS properties of aqueous solutions of antibody–poly(methacrylic acid) and antibody–poly(acrylic acid) conjugates and solutions of their components [antibody, poly(methacrylic acid), and poly(acrylic acid)] at different pH values have been measured. In both cases the parallel comparison of the characteristic size variations allowed us to represent novel structural features of scattered particles (macromolecules, associates, aggregates, conjugates, colloidal particles) in studied systems.     

Transport Properties of Nonelectrolyte Liquid Mixtures. XI. Mutual Diffusion Coefficients for Toluene+n-Hexane and Toluene+Acetonitrile at Temperatures from 273 to 348 K and at Pressures up to 25 MPa

Mutual diffusion coefficients,D ₁₂, have been measured at pressures up to 25 MPa using the chromatographic peak broadening technique (Taylor dispersion method) forxtoluene+(1–x)n-hexane in the temperature range 298 to 348 K and forxtoluene+(1–x) acetonitrile in the temperature range 273 to 348 K. The estimated uncertainty is ±4%. Both systems show negative deviations from straight-line behavior. The fractional decrease inD ₁₂is about 0.8% per MPa. Hard-sphere theory is applied under limiting conditions where one of the components is present in a trace amount. It is shown that the diffusion coefficients can be estimated by the Dullien method from a knowledge of the viscosity and density under the same conditions.     

Standardization of Light Scattering Measurement in Conjunction With Immunochemical Analysis

Light scattering methods for the physical analysis of synthetic and biological polymers necessitates the use of scattering standards and absolute light scattering measurements. Standardization has not been employed when light scattering has been used to monitor immunochemical reactions using a kinetic or thermodynamic mode.The concentration of a specific protein present in a complex matrix such as urine, serum or cerebrospinal fluid, is measured by reacting the protein of interest with its specific antibody and then measuring the excess light scattering of the solution produced by the formation of antigen antibody complexes. The lack of established light scattering standards in the area of immunochemical measurements makes instrumental quality control difficult and has hindered direct comparison of data among investigators. Both solid and liquid light scattering standards would be necessary to encompass the wide range of instrumentation currently in use. Several solid standards which have been used in the past include reflecting diffusers such as vitrolite, magnesium carbonate crystals with a ground surface, magnesium oxide coatings on magnesium carbonate crystal, casein paint on vitrolite, and solid opal glass transmitting diffusers such as flashed opal glass and solid opal glass. These standards, while applicable to manual light scattering photometers, are not suitable for recently developed automated instrumentation. Liquid standards in the form of Ludox^®, solutions of polystyrene, suspensions of small diameter latex spheres and even pure organic solvents could be used more easily with the continuous flow and discrete automated analyzers. The introduction of instrumental standards at this level of analysis would result in improved overall quality control and facilitate data and method comparison between laboratories.     

Thermophysical Properties of the Refrigerant Mixtures R410A and R407C from Dynamic Light Scattering (DLS)

Dynamic light scattering (DLS) has been used for the measurement of several thermophysical properties of the refrigerant mixtures R410A and R407C. Thermal diffusivity and sound speed have been obtained by light scattering from bulk fluids for both the liquid and vapor phases under saturation conditions over a temperature range from about 290 K up to the liquid-vapor critical point. By applying the method of DLS to a liquid-vapor interface, also called surface light scattering (SLS), the saturated liquid kinematic viscosity and surface tension can be determined simultaneously. These properties have been measured for R410A and R407C from about 240 to 330 K and 240 to 350 K, respectively. The results are discussed in detail in comparison with literature data and with a simple prediction method based on the mass-weighted properties of the pure components expressed as functions of the reduced temperature.     

用Stopped-flow光散射方法研究NaCl浓度对CTAB棒状胶束形态转变的影响

用Stopped-flow光散射方法研究NaCl浓度对CTAB（十六烷基三甲基溴化铵）棒状胶束形态转变的影响。对同一CTAB溶液体系增加盐浓度，或者保持盐浓度恒定条件下增加CTAB浓度，胶束形态都出现显著的从球状到棒状转变过程。     

Infinite-Dilution Binary Diffusion Coefficients of 2-Propanone, 2-Butanone, 2-Pentanone, and 3-Pentanone in CO2 by the Taylor Dispersion Technique from 308.15 to 328.15 K in the Pressure Range from 8 to 35 MPa

Infinite-dilution binary diffusion coefficients of 2-propanone, 2-butanone, 2-pentanone, and 3-pentanone in carbon dioxide were measured by the Taylor dispersion method at temperatures from 308.15 to 328.15 K and pressures from 7.60 to 34.57 MPa. The D₁₂ values were obtained from the response curves by the method of fitting in the time domain. The accuracy in the fitting error was examined for each measurement. The measured D₁₂ data were found to be well correlated by the Schmidt number correlation, with AAD%=3.74% for all solutes.     

激光光散射法表征人用皮卡狂犬病疫苗分子量与人体副反应关系的观察

为了解人用皮卡狂犬病疫苗分子量与人体副反应的关系,用激光光散射法进行了实验。结果表明：当疫苗中皮卡浓度为１１．９５ｍ ｇ／ｍ ｌ时,其重均分子量Ｍ ｗ ＝ ２９．６×１０４,２０名志愿者中７人出现局部和全身过敏反应;当疫苗中皮卡浓度为１ｍ ｇ／ｍ ｌ时,其重均分子量Ｍｗ ＝ ５．６×１０４,２０名志愿者中无一人出现接种后副反应。这说明,用激光光散射法检测人用皮卡狂犬病疫苗分子量的大小与人体副反应的关系密切。     

Measurements of the Liquid Viscosities of Mixtures of n-Butane, n-Hexane, and n-Octane with Squalane to 30 MPa

The viscosities of liquid mixtures of n-butane, n-hexane, and n-octane with squalane that represent model mixtures of refrigerants with refrigeration oil were measured at temperatures between 273.15 and 333.15 K, and at pressures from 0.1 to 30 MPa, by using a falling body viscometer. The uncertainty of the measurements was estimated to be no larger than 2.9%. The experimental viscosity values were fitted to a Tait-like equation within 2.8%. There are larger deviations between the experimental data and calculated values predicted by the equation of Kanti et al., which is derived from the Flory theory. By introducing an interaction parameter of the energetic mixing rule into the equation, the deviations were significantly reduced.     

Measurement of mode I and mode II rock dynamic fracture toughness with cracked straight through flattened Brazilian disc impacted by split Hopkinson pressure bar

In order to find an effective and convincing method to measure rock dynamic fracture toughness for mode I and mode II, cracked straight through flattened Brazilian disc specimens of marble, which were geometrically similar for three size, were diametrically impacted by split Hopkinson pressure bar on the flat end of the specimen with three load angle respectively. History of stress intensity factors (K_I(t) for opening mode I, and K_II(t) for sliding mode II), mode mixture ratio (K_I(t)/K_II(t)), as well as mode I and mode II dynamic fracture toughness at crack initiation (K_Id and K_IId) were determined with the experimental–numerical method. It is found that there is a unique size effect for dynamic fracture test with the specimens, the mode mixture ratio is not solely determined by load angle (the angle between load direction and crack line) as in the static loading; the pure mode II load angle is 19° for the ?50 mm specimen, however it is 10° for the ?130 mm and ?200 mm specimens; the mode II load angle decreases with increment of specimen size. Realization of pure mode II is justified by the mode mixture ratio approaching zero, it can be realized under certain load angle and loading rate for the specimen of specified size. K_IId is generally greater than K_Id. Both K_Id and K_IId increase with increment of specimen size, and this trend for K_IId is more remarkable than that for K_Id.