Forced Rayleigh Scattering Research Articles

Thermophoretic microfluidic cells for evaluating Soret coefficient of colloidal particles

Thermodiffusion or thermophoresis gained much interest in bio, chemical, and energy engineering. Although there are several methods to measure thermophoresis, they consume large sample volumes, are limited to binary mixtures, and give only indirect access to the applied temperature profile. Herein, we propose a thermophoretic microfluidic cell for quantitative measurements of the Soret coefficient of colloids. The actual microscale measuring channel lies between cooling and heating channels to achieve a one-dimensional temperature gradient. Fluorescence lifetime imaging microscopy with Rhodamine B is utilized to measure the spatial temperature profile in the channel. The fluorescence intensity of fluorescently labeled polystyrene particles with a diameter of 25 nm is used to monitor the concentration profile. The observed temperature and concentration profiles are one-dimensional, as gradients in the longitudinal and height directions can be neglected. In the investigated temperature range, the averaged difference between the measured Soret coefficients with the cell and determined with the Thermal Diffusion Forced Rayleigh Scattering set-up is less than 8%.

Effect of an excess of surfactant on thermophoresis, mass diffusion and viscosity in an oily surfactant-stabilized ferrofluid.

The effect of an excess of surfactant on the thermophoresis of a sterically stabilized ferrofluid is investigated experimentally by forced Rayleigh scattering (FRS). The experiments are performed with a stable magnetic fluid sample to which controlled amounts of surfactant are added. A decrease in the thermally induced transport of magnetic nanoparticles is observed while increasing the temperature T. The positive Soret coefficient [Formula: see text] decreases by adding 2vol% of surfactant at room temperature. As shown by FRS relaxation, this decreasing is mainly associated with a reduction of the interaction between the carrier fluid and individual nanoparticles. No significant effect of extra surfactant on the sign of [Formula: see text] is observed at higher T's (up to [Formula: see text]C). Dynamic light scattering at room temperature reveals the presence of a small amount of clusters/aggregates in the samples, which are hardly detectable by FRS relaxation. The presence of these small clusters/aggregates is confirmed by a rheological probing of the fluid properties. Whatever T, a small amount of added surfactant first causes a decrease of the ferrofluid viscosity, associated with a 10% decreasing of the flow activation energy. Further on, viscosity and activation energy both recover at higher excess surfactant concentrations. These results are analyzed in terms of saturation of the surfactant layer, concentration of free surfactant chains and heat of transport of the nanoparticles.

Towards understanding specific ion effects in aqueous media using thermodiffusion

Specific ion effects play an important role in scientific and technological processes. According to Hofmeister, the influence on the hydrogen bond network depends on the ion and leads to a specific order of the ions. Also thermodiffusion the mass transport caused by a temperature gradient is very sensitive to changes of the hydrogen bond network leading to a ranking according to hydrophilicity of the salt. Hence, we investigate various salt solutions in order to compare with the Hofmeister concept. We have studied three different sodium salts in water as a function of temperature (25–45^circ C) and concentration (0.5–5 mol kg^{-1}) using Thermal Diffusion Forced Rayleigh Scattering (TDFRS). The three anions studied, carbonate, acetate and thiocyanate, span the entire range of the Hofmeister series from hydrophilic to hydrophobic. We compare the results with the recent measurements of the corresponding potassium salts to see to what extent the cation changes the thermodiffusion of the salt.Graphic abstract

Bridging dynamic regimes of segmental relaxation and center-of-mass diffusion in associative protein hydrogels

Molecular transport in dense, crowded media is often affected by binding and collisions with obstacles, leading to complex spatial distributions and anomalous diffusion on multiple length scales. Here, neutron spin-echo (NSE) spectroscopy and forced Rayleigh scattering (FRS) were used in tandem to study the interplay between segmental and center-of-mass chain dynamics in the presence of strong binding interactions in a model protein hydrogel. The results provide evidence for several dynamic scaling regimes of gel relaxation behavior with varying length scale, including a caging regime bridging submolecular relaxation and center-of-mass diffusion due to transient binding. On mesoscopic length scales larger than the size of the cage, chains undergo two distinct regimes of apparent superdiffusive scaling, with different power-law exponents, before the onset of terminal Fickian diffusion. The combined NSE and FRS results are interpreted in the context of prior Brownian dynamics simulations of associating star polymers, revealing insight into structural length scales and binding kinetics governing the transition from segmental relaxation to self-diffusion in the protein hydrogel. Finally, single-sticker tracer diffusion measurements were performed to directly probe sticker association/dissociation dynamics within the gel, the results suggesting that cooperative cluster motion may play a role in network relaxation on larger length scales.Received 28 February 2020Accepted 30 October 2020DOI:https://doi.org/10.1103/PhysRevResearch.2.043369Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasDiffusionPhysical SystemsPolymer gelsTechniquesLight scatteringNeutron scatteringNeutron spin echo spectroscopyPolymers & Soft Matter

Correlation between thermophoretic behavior and hydrophilicity for various alcohols⋆.

Recent experiments for various amides and sugars showed a clear correlation of the temperature dependence of the Soret coefficient with the hydrophilicity, quantitatively described by the logarithm of the 1-octanol/water partition coefficient logP . This coefficient is a measure for the hydrophilicity/hydrophobicity balance of a solute and is often used to model the transport of a compound in the environment or to screen for potential pharmaceutical compounds. In order to validate whether this concept works also for other water soluble molecules we investigated systematically the thermophoresis of mono- and polyhydric alcohols. As experimental method we use a holographic grating technique called infrared Thermal Diffusion Forced Rayleigh Scattering (IR-TDFRS). Experiments showed that the temperature dependence of the Soret coefficient of polyhydric alcohols also correlates with logP and lies on the same master plot as amides and sugars.

Study of diffusion in bulk polymer films below glass transition: evidences of dynamical heterogeneities

By means of the Forced Rayleigh Scattering (holographic grating relaxation) technique the diffusion of dye molecules in bulk films of polymer below entanglement molecular weight was investigated around the glass transition temperature. In the temperature range [Tg–20К; Tg+ 5К] a splitting of the dye diffusion coefficient into two separate branches was revealed. The phenomenon was found to be similar to that reported for thin polymer films, which may prove the dominating role of dynamic heterogeneities in the investigated temperature region.

2波長観察用レーザーを利用したソーレー強制レイリー散乱法による3成分系のソーレー係数・熱拡散係数測定法の開発

2波長観察用レーザーを利用したソーレー強制レイリー散乱法による3成分系のソーレー係数・熱拡散係数測定法の開発

Influence of temperature and charge effects on thermophoresis of polystyrene beads⋆.

We study the thermodiffusion behavior of spherical polystyrene beads with a diameter of 25 nm by infrared thermal diffusion Forced Rayleigh Scattering (IR-TDFRS). Similar beads were used to investigate the radial dependence of the Soret coefficient by different authors. While Duhr and Braun (Proc. Natl. Acad. Sci. U.S.A. 104, 9346 (2007)) observed a quadratic radial dependence Braibanti et al. (Phys. Rev. Lett. 100, 108303 (2008)) found a linear radial dependence of the Soret coefficient. We demonstrated that special care needs to be taken to obtain reliable thermophoretic data, because the measurements are very sensitive to surface properties. The colloidal particles were characterized by transmission electron microscopy and dynamic light scattering (DLS) experiments were performed. We carried out systematic thermophoretic measurements as a function of temperature, buffer and surfactant concentration. The temperature dependence was analyzed using an empirical formula. To describe the Debye length dependence we used a theoretical model by Dhont. The resulting surface charge density is in agreement with previous literature results. Finally, we analyze the dependence of the Soret coefficient on the concentration of the anionic surfactant sodium dodecyl sulfate (SDS), applying an empirical thermodynamic approach accounting for chemical contributions.

Classical Challenges in the Physical Chemistry of Polymer Networks and the Design of New Materials.

Polymer networks are widely used from commodity to biomedical materials. The space-spanning, net-like structure gives polymer networks their advantageous mechanical and dynamic properties, the most essential factor that governs their responses to external electrical, thermal, and chemical stimuli. Despite the ubiquity of applications and a century of active research on these materials, the way that chemistry and processing interact to yield the final structure and the material properties of polymer networks is not fully understood, which leads to a number of classical challenges in the physical chemistry of gels. Fundamentally, it is not yet possible to quantitatively predict the mechanical response of a polymer network based on its chemical design, limiting our ability to understand and characterize the nanostructure of gels and rationally design new materials. In this Account, we summarize our recent theoretical and experimental approaches to study the physical chemistry of polymer networks. First, our understanding of the impact of molecular defects on topology and elasticity of polymer networks is discussed. By systematically incorporating the effects of different orders of loop structure, we develop a kinetic graph theory and real elastic network theory that bridge the chemical design, the network topology, and the mechanical properties of the gel. These theories show good agreement with the recent experimental data without any fitting parameters. Next, associative polymer gel dynamics is discussed, focusing on our evolving understanding of the effect of transient bonds on the mechanical response. Using forced Rayleigh scattering (FRS), we are able to probe diffusivity across a wide range of length and time scales in gels. A superdiffusive region is observed in different associative network systems, which can be captured by a two-state kinetic model. Further, the effects of the architecture and chemistry of polymer chains on gel nanostructure are studied. By incorporating shear-thinning coiled-coil protein motifs into the midblock of a micelle-forming block copolymer, we are able to responsively adjust the gel toughness through controlling the nanostructure. Finally, we review the development of novel application-oriented materials that emerge from our enhanced understanding of gel physical chemistry, including injectable gel hemostats designed to treat internal wounds and engineered nucleoporin-like polypeptide (NLP) hydrogels that act as biologically selective filters. We believe that the fundamental physical chemistry questions articulated in this Account will provide inspiration to fully understand the design of polymer networks, a group of mysterious yet critically important materials.

Accumulation of formamide in hydrothermal pores to form prebiotic nucleobases

Formamide is one of the important compounds from which prebiotic molecules can be synthesized, provided that its concentration is sufficiently high. For nucleotides and short DNA strands, it has been shown that a high degree of accumulation in hydrothermal pores occurs, so that temperature gradients might play a role in the origin of life [Baaske P, et al. (2007)Proc Natl Acad Sci USA104(22):9346-9351]. We show that the same combination of thermophoresis and convection in hydrothermal pores leads to accumulation of formamide up to concentrations where nucleobases are formed. The thermophoretic properties of aqueous formamide solutions are studied by means of Infrared Thermal Diffusion Forced Rayleigh Scattering. These data are used in numerical finite element calculations in hydrothermal pores for various initial concentrations, ambient temperatures, and pore sizes. The high degree of formamide accumulation is due to an unusual temperature and concentration dependence of the thermophoretic behavior of formamide. The accumulation fold in part of the pores increases strongly with increasing aspect ratio of the pores, and saturates to highly concentrated aqueous formamide solutions of ∼85 wt% at large aspect ratios. Time-dependent studies show that these high concentrations are reached after 45-90 d, starting with an initial formamide weight fraction of[Formula: see text]wt % that is typical for concentrations in shallow lakes on early Earth.

Thermodiffusion, molecular diffusion and Soret coefficient of binary and ternary mixtures of n-hexane, n-dodecane and toluene.

In this study, the thermodiffusion, molecular diffusion, and Soret coefficients of 12 binary mixtures composed of toluene, n-hexane and n-dodecane in the whole range of concentrations at atmospheric pressure and temperatures of 298.15 K and 308.15 K have been determined. The experimental measurements have been carried out using the Thermogravitational Column, the Sliding Symmetric Tubes and the Thermal Diffusion Forced Rayleigh Scattering techniques. The results obtained using the different techniques show a maximum deviation of 9% for the thermodiffusion coefficient, 8% for the molecular diffusion coefficient and 2% for the Soret coefficient. For the first time we report a decrease of the thermodiffusion coefficient with increasing ratio of the thermal expansion coefficient and viscosity for a binary mixture of an organic ring compound with a short n-alkane. This observation is discussed in terms of interactions between the different components. Additionally, the thermogravitational technique has been used to measure the thermodiffusion coefficients of four ternary mixtures consisting of toluene, n-hexane and n-dodecane at 298.15 K. In order to complete the study, the values obtained for the molecular diffusion coefficient in binary mixtures, and the thermodiffusion coefficient of binary and ternary mixtures have been compared with recently derived correlations.

How does thermodiffusion of aqueous solutions depend on concentration and hydrophobicity?

The thermal diffusion of aqueous solutions of mono-, di-ethylene glycols, poly(ethylene glycol), methanol, and glycerol is investigated systematically as a function of concentration using the Thermal Diffusion Forced Rayleigh Scattering (TDFRS). For all investigated binary mixtures, the Soret coefficient, S(T), decays with increasing concentration of the non-aqueous component showing two regions. For aqueous solution of ethylene glycol, at a very low solute content the decay is steep, while it becomes less steep for higher solute concentration. All mixtures show a sign change of S(T) with concentration. The sign change concentration is discussed with respect to chemical structures of solute molecules and the partition coefficient, log p. It turns out that the number of hydroxyl groups plays an important role. For the investigated aqueous mixtures, we find empirical linear relations between the sign change concentration and the ratio of the number of hydroxyl groups to the number of carbon atoms as well as the partition coefficient, log p.

Investigation of Anisotropic Thermal Conductivity in Polymers Using Infrared Thermography

A new experimental method based on infrared thermography (IRT) is developed to study deformation-induced anisotropic thermal conductivity in polymers. An analytic solution for the temperature field of samples heated by a point source is utilized with a robust fitting procedure allowing for quantitative measurement of two components of the normalized thermal conductivity tensor of uniaxially stretched samples. In order to validate the method, we compare measurements on a cross-linked polybutadiene network with those obtained from a previously developed technique based on forced Rayleigh scattering (FRS). We find excellent agreement between the two techniques. Uncertainty in the measurements using IRT method is estimated to be about 2–5%. The accuracy of the method and its potential application to nontransparent materials make it a good alternative to extend current research on anisotropic thermal transport in polymeric materials.

G134 ソーレー強制レイリー散乱法による3成分系溶液の交差拡散係数及びソーレー係数測定法の開発 : 2波長観察用レーザーを用いた測定理論

G134 ソーレー強制レイリー散乱法による3成分系溶液の交差拡散係数及びソーレー係数測定法の開発 : 2波長観察用レーザーを用いた測定理論

ソーレー強制レイリー散乱法を用いた燃料電池用電解質膜内メタノール水溶液の拡散係数測定法の開発

直接メタノール型燃料電池は携帯機器用等の電源として注目されているが，重要な課題としてメタノールクロスオーバーがある．評価手法として膜内拡散センシングが必要とされているがその手法は確立されていない．そこで非接触・msオーダーで相互拡散係数を測定できるCO2レーザーを用いたソーレー強制レイリー散乱法(Soret forced Rayleigh scattering method: SFRS)の適用を試みた．本研究では電解質膜に適用する際の問題点とヘテロダイン検知等による解決策を提示し，装置構築を行った上でNafion 117内13wt%メタノール水溶液の拡散係数の予備的な測定結果が得られたので報告する．

Structuralization of Magnetic Nanoparticles Induced by Laser Heating in Magnetic Fluids

The structuralization of magnetic particles in magnetic fluids due to the thermodiffusion induced by laser light illumination was experimentally observed in two types of magnetic fluids: one based on a mineral oil with magnetite particles covered by a monolayer of oleic acid as a surfactant and the other a kerosene-based magnetic fluid sterically stabilized by a double layer consisting of oleic acid and dodecylbenzenesulphonic acid (DBS). Forced Rayleigh scattering (FRS) showed different behaviors of magnetic particle structuralization in the observed magnetic fluids. While for the case of mineral oil-based magnetic fluids, there was observed a positive thermodiffusion (S > 0), an indication of negative thermodiffusion (S < 0) was observed in magnetic fluids based on kerosene. This was also confirmed by the time-dependent decay of a grating of magnetic particles. Numerical simulation of aggregation for the case of negative thermodiffusion was confirmed by the observed aggregation after laser illumination in kerosene-based magnetic fluids and enabled an estimated value of the negative Soret constant in the magnetic fluid studied (S ≈ −10−2 K−1).

Mass Diffusion Coefficients of Cellulose Acetate Butyrate in Methyl Ethyl Ketone Solutions at Temperatures between (293 and 323) K and Mass Fractions from 0.05 to 0.60 Using the Soret Forced Rayleigh Scattering Method

The binary mass diffusion coefficients of cellulose acetate butyrate in methyl ethyl ketone solutions (CAB + MEK) have been measured under atmospheric pressure at temperatures from (293 to 323) K and mass fractions from 0.05 to 0.6. The present experimental apparatus is based on the Soret forced Rayleigh scattering method (S-FRSM), which utilizes the Soret effect to create periodic spatial concentration modulation of micrometer-order fringe spacing in a sample binary liquid mixture due to the absorption of an optical interference grating generated by two intersecting heating laser beams. The decay of the concentration modulation by the mass diffusion process is monitored by the diffraction of a probing laser beam. This method provides several advantages in comparison with conventional techniques such as Taylor dispersion or diaphragm cells; namely, a single measurement can be performed within a short time [(10−3 to 10−2) s], with small temperature and concentration changes (ΔT < 10−2 K and Δc < 10−5) usin...

Real-Time Sensing of the Thermal Diffusivity for Dynamic Control of Anisotropic Heat Conduction of Liquid Crystals

Molecular orientational order can be used to characterize the anisotropic behavior in mechanical, optical, and thermophysical properties. The creation of appropriate molecular orientation has the potential for producing a novel material or thermal switching device, which can control anisotropic heat conduction. Liquid crystals, which are widely used in display elements, have anisotropy not only in their optical, but also in their thermophysical properties, under given molecular orientational alignment conditions; this material can be a variable device with anisotropic heat conduction by controlling the molecular alignment. In the present study, a real-time sensing system for thermal diffusivity using the forced Rayleigh scattering (FRS) method was developed to investigate the transient behavior in the thermal anisotropy of nematic liquid crystals. This technique can be used to measure the in-plane thermal diffusivity perpendicular to the transient thermal grating created by interfering pulsed laser beams, and the thermal anisotropy of the sample can be determined using this non-contact method. The present FRS system can provide continuous measurements of the thermal diffusivity with subsecond time resolution, allowing evaluation of the dynamic behavior of anisotropy in the thermal diffusivity even during a transient process. In this article, the anisotropy of the in-plane thermal diffusivity of 4-4′-pentyl-4-biphenylcarbonitrile (5CB) with molecular alignment induced by either a rubbed substrate or an electric field has been measured. Also, the time evolution of the anisotropic thermal diffusivity in real-time under a dynamically controlled external electric field has been measured. The experimental results demonstrate the capability of dynamic anisotropic control of heat conduction by molecular alignment variations.

Tracer diffusion properties of core–shell latex films studied by photoinduced grating relaxation

AbstractThis article reports the application of the Photo‐Induced Grating Relaxation technique (also known as Forced Rayleigh Scattering) to investigate the dynamics of films prepared from structured core–shell latex particles via the transport property of the photochromic tracer molecule Aberchrome 540®. The core–shell particles were prepared with a fluoropolymer core (immiscible and impenetrable to the tracer) and a poly(butyl methacrylate) shell. The incompletely dried films (with residual water) manifest their spatial heterogeneity via non‐Fickian behavior (spatial scale‐ dependent apparent diffusion coefficient). The diffusion data was interpreted using the two‐state diffusion model, previously developed to describe the tracer diffusion in latex films without any core–shell structure. In contrast to dry latex films made from homogeneous particles, where one observes Fickian diffusion indicative of a homogeneous polymer film, we find that the lattice of fluoropolymer cores leads to a length scale dependent diffusion coefficient for the tracer. This effect can be interpreted as microscopic evidence for a strain hardening effect due to the presence of a hardened layer of matrix polymer (= shell) surrounding the core, which act as nanofillers. This strain hardening effect could be quantified within the two‐state diffusion model in terms of tracer diffusion coefficients and root mean squared displacements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2823–2834, 2007

Experimental Determination of the Soret Coefficient of Ionic Ferrofluids: Influence of the Volume Fraction and Ionic Strength

Forced Rayleigh scattering (FRS) is a powerful technique for investigating heat and mass transfers in colloids. In the present work, we determine the Soret coefficient ST and the thermal diffusion coefficient DT of magnetic colloids (ferrofluids). It has been theoretically predicted that the thermal diffusion coefficient DT of colloids depends both on the particle–solvent interfacial interaction and on the interactions between the colloidal particles. In order to understand the microscopic behavior of the Soret effect in these ionic magnetic colloids, experiments are performed on aqueous samples of various volume fractions Φ and ionic strengths. The dominant effect on the Soret coefficient comes from the particle–solvent interaction and determines its sign. Interparticle interactions have an influence on ST in the moderate concentration range where virial-like expansions are possible. In this range (Φ ≤ 0.10) and within the experimental error bars, the thermal diffusion does not depend on the ionic strength of the dispersion, and the Φ-dependence of the friction coefficient is comparable to that of hard spheres. At larger concentrations, the thermal diffusion drastically decreases as the colloid approaches its dynamical glass transition.