Conduction-only transport phenomena in compressible bivelocity fluids: diffuse interfaces and Korteweg stresses.

"Diffuse interface" theories for single-component fluids­dating back to van der Waals, Korteweg, Cahn-Hilliard, and many others­are currently based upon an ad hoc combination of thermodynamic principles (built largely upon Helmholtz's free-energy potential) and so-called "nonclassical" continuum-thermomechanical principles (built largely upon Newtonian mechanics), with the latter originating with the pioneering work of Dunn and Serrin [Arch. Ration. Mech. Anal. 88, 95 (1985)]. By introducing into the equation governing the transport of energy the notion of an interstitial work-flux contribution, above and beyond the usual Fourier heat-flux contribution, namely, jq = -k∇T, to the energy flux, Dunn and Serrin provided a rational continuum-thermomechanical basis for the presence of Korteweg stresses in the equation governing the transport of linear momentum in compressible fluids. Nevertheless, by their failing to recognize the existence and fundamental need for an independent volume transport equation [Brenner, Physica A 349, 11 (2005)]­especially for the roles played therein by the diffuse volume flux j v and the rate of production of volume πν at a point of the fluid continuum­we argue that diffuse interface theories for fluids stand today as being both ad hoc and incomplete owing to their failure to recognize the need for an independent volume transport equation for the case of compressible fluids. In contrast, we point out that bivelocity hydrodynamics, as it already exists [Brenner, Phys. Rev. E 86, 016307 (2012)], provides a rational, non-ad hoc, and comprehensive theory of diffuse interfaces, not only for single-component fluids, but also for certain classes of crystalline solids [Danielewski and Wierzba, J. Phase Equilib. Diffus. 26, 573 (2005)]. Furthermore, we provide not only what we believe to be the correct constitutive equation for the Korteweg stress in the class of fluids that are constitutively Newtonian in their rheological response to imposed stresses but, equally importantly, we establish the explicit functional forms of Korteweg's phenomenological thermocapillary coefficients appearing therein.

Multiplex particle focusing via hydrodynamic force in viscoelastic fluids.

We introduce a multiplex particle focusing phenomenon that arises from the hydrodynamic interaction between the viscoelastic force and the Dean drag force in a microfluidic device. In a confined microchannel, the first normal stress difference of viscoelastic fluids results in a lateral migration of suspended particles. Such a viscoelastic force was harnessed to focus different sized particles in the middle of a microchannel, and spiral channel geometry was also considered in order to take advantage of the counteracting force, Dean drag force that induces particle migration in the outward direction. For theoretical understanding, we performed a numerical analysis of viscoelastic fluids in the spiral microfluidic channel. From these results, a concept of the 'Dean-coupled Elasto-inertial Focusing band (DEF)' was proposed. This study provides in-depth physical insight into the multiplex focusing of particles that can open a new venue for microfluidic particle dynamics for a concrete high throughput platform at microscale.

Fullerene embedded shape memory nanolens array.

Securing fragile nanostructures against external impact is indispensable for offering sufficiently long lifetime in service to nanoengineering products, especially when coming in contact with other substances. Indeed, this problem still remains a challenging task, which may be resolved with the help of smart materials such as shape memory and self-healing materials. Here, we demonstrate a shape memory nanostructure that can recover its shape by absorbing electromagnetic energy. Fullerenes were embedded into the fabricated nanolens array. Beside the energy absorption, such addition enables a remarkable enhancement in mechanical properties of shape memory polymer. The shape memory nanolens was numerically modeled to impart more in-depth understanding on the physics regarding shape recovery behavior of the fabricated nanolens. We anticipate that our strategy of combining the shape memory property with the microwave irradiation feature can provide a new pathway for nanostructured systems able to ensure a long-term durability.

Proposal of a critical test of the Navier-Stokes-Fourier paradigm for compressible fluid continua.

A critical, albeit simple experimental and/or molecular-dynamic (MD) simulation test is proposed whose outcome would, in principle, establish the viability of the Navier-Stokes-Fourier (NSF) equations for compressible fluid continua. The latter equation set, despite its longevity as constituting the fundamental paradigm of continuum fluid mechanics, has recently been criticized on the basis of its failure to properly incorporate volume transport phenomena-as embodied in the proposed bivelocity paradigm [H. Brenner, Int. J. Eng. Sci. 54, 67 (2012)]-into its formulation. Were the experimental or simulation results found to accord, even only qualitatively, with bivelocity predictions, the temperature distribution in a gas-filled, thermodynamically and mechanically isolated circular cylinder undergoing steady rigid-body rotation in an inertial reference frame would not be uniform; rather, the temperature would be higher at the cylinder wall than along the axis of rotation. This radial temperature nonuniformity contrasts with the uniformity of the temperature predicted by the NSF paradigm for these same circumstances. Easily attainable rates of rotation in centrifuges and readily available tools for measuring the expected temperature differences render experimental execution of the proposed scheme straightforward in principle. As such, measurement-via experiment or MD simulation-of, say, the temperature difference ΔT between the gas at the wall and along the axis of rotation would provide quantitative tests of both the NSF and bivelocity hydrodynamic models, whose respective solutions for the stated set of circumstances are derived in this paper. Independently of the correctness of the bivelocity model, any temperature difference observed during the proposed experiment or simulation, irrespective of magnitude, would preclude the possibility of the NSF paradigm being correct for fluid continua, except for incompressible flows.

Thermal and viscous effects on sound waves: revised classical theory.

In this paper the recently developed, bi-velocity model of fluid mechanics based on the principles of linear irreversible thermodynamics (LIT) is applied to sound propagation in gases taking account of first-order thermal and viscous dissipation effects. The results are compared and contrasted with the classical Navier-Stokes-Fourier results of Pierce for this same situation cited in his textbook. Comparisons are also made with the recent analyses of Dadzie and Reese, whose molecularly based sound propagation calculations furnish results virtually identical with the purely macroscopic LIT-based bi-velocity results below, as well as being well-supported by experimental data. Illustrative dissipative sound propagation examples involving application of the bi-velocity model to several elementary situations are also provided, showing the disjoint entropy mode and the additional, evanescent viscous mode.

Predicting enhanced mass flow rates in gas microchannels using nonkinetic models.

Different nonkinetic approaches are adopted in this paper towards theoretically predicting the experimentally observed phenomenon of enhanced mass flow rates accompanying pressure-driven rarefied gas flows through microchannels. Our analysis utilizes a full set of mechanically consistent volume-diffusion hydrodynamic equations, allowing complete, closed-form, analytical solutions to this class of problems. As an integral part of the analysis, existing experimental data pertaining to the subatmospheric pressure dependence of viscosity were analyzed. The several nonkinetic approaches investigated were (1) pressure-dependent viscosity exponent model, (2) slip-velocity models, and (3) volume diffusion model. We explored the ability to predict the gas's mass flow rate over the full range of Knudsen numbers, including furnishing a physically sound interpretation of the well-known Knudsen minimum observed in the mass flow rate. Matching of a pressure-dependent viscosity model, one that follows the standard temperature-viscosity power law and its supporting single momentum diffusion mechanism, did not allow an accurate interpretation of the data. Rather, matching of this model with the flow rate was found to mismatch the experimental pressure dependence of the viscosity. An additional transport mechanism model, one based on volume diffusion, offered a comprehensive understanding of the Knudsen minimum, while also resulting in excellent agreement with experimental data well into the transition regime (up to a Knudsen number of 5).

Fluid mechanics in fluids at rest.

Using readily available experimental thermophoretic particle-velocity data it is shown, contrary to current teachings, that for the case of compressible flows independent dye- and particle-tracer velocity measurements of the local fluid velocity at a point in a flowing fluid do not generally result in the same fluid velocity measure. Rather, tracer-velocity equality holds only for incompressible flows. For compressible fluids, each type of tracer is shown to monitor a fundamentally different fluid velocity, with (i) a dye (or any other such molecular-tagging scheme) measuring the fluid's mass velocity v appearing in the continuity equation and (ii) a small, physicochemically and thermally inert, macroscopic (i.e., non-Brownian), solid particle measuring the fluid's volume velocity v(v). The term "compressibility" as used here includes not only pressure effects on density, but also temperature effects thereon. (For example, owing to a liquid's generally nonzero isobaric coefficient of thermal expansion, nonisothermal liquid flows are to be regarded as compressible despite the general perception of liquids as being incompressible.) Recognition of the fact that two independent fluid velocities, mass- and volume-based, are formally required to model continuum fluid behavior impacts on the foundations of contemporary (monovelocity) fluid mechanics. Included therein are the Navier-Stokes-Fourier equations, which are now seen to apply only to incompressible fluids (a fact well-known, empirically, to experimental gas kineticists). The findings of a difference in tracer velocities heralds the introduction into fluid mechanics of a general bipartite theory of fluid mechanics, bivelocity hydrodynamics [Brenner, Int. J. Eng. Sci. 54, 67 (2012)], differing from conventional hydrodynamics in situations entailing compressible flows and reducing to conventional hydrodynamics when the flow is incompressible, while being applicable to both liquids and gases.

Beyond the no-slip boundary condition.

This paper offers a simple macroscopic approach to the question of the slip boundary condition to be imposed upon the tangential component of the fluid velocity at a solid boundary. Plausible reasons are advanced for believing that it is the energy equation rather than the momentum equation that determines the correct fluid-mechanical boundary condition. The scheme resulting therefrom furnishes the following general, near-equilibrium linear constitutive relation for the slip velocity of mass along a relatively flat wall bounding a single-component gas or liquid: (v(m))(slip)=-α∂lnρ/∂s|(wall), where α and ρ are, respectively, the fluid's thermometric diffusivity and mass density, while the length δs refers to distance measured along the wall in the direction in which the slip or creep occurs. This constitutive relation is shown to agree with experimental data for gases and liquids undergoing thermal creep or pressure-driven viscous creep at solid surfaces.

Phoresis in fluids.

This paper presents a unified theory of phoretic phenomena in single-component fluids. Simple formulas are given for the phoretic velocities of small inert force-free non-Brownian particles migrating through otherwise quiescent single-component gases and liquids and animated by a gradient in the fluid's temperature (thermophoresis), pressure (barophoresis), density (pycnophoresis), or any combination thereof. The ansatz builds upon a recent paper [Phys. Rev. E 84, 046309 (2011)] concerned with slip of the fluid's mass velocity at solid surfaces--that is, with phenomena arising from violations of the classical no-slip fluid-mechanical boundary condition. Experimental and other data are cited in support of the phoretic model developed herein.

A critical test of bivelocity hydrodynamics for mixtures.

The present paper provides direct noncircumstantial evidence in support of the existence of a diffuse flux of volume j(v) in mixtures. As such, it supersedes an earlier paper [H. Brenner, J. Chem. Phys. 132, 054106 (2010)], which offered only indirect circumstantial evidence in this regard. Given the relationship of the diffuse volume flux to the fluid's volume velocity, this finding adds additional credibility to the theory of bivelocity hydrodynamics for both gaseous and liquid continua, wherein the term bivelocity refers to the independence of the fluid's respective mass and volume velocities. Explicitly, the present work provides a new and unexpected linkage between a pair of diffuse fluxes entering into bivelocity mixture theory, fluxes that were previously regarded as constitutively independent, except possibly for their coupling arising as a consequence of Onsager reciprocity. In particular, for the case of a binary mixture undergoing an isobaric, isothermal, external force-free, molecular diffusion process we establish by purely macroscopic arguments-while subsequently confirming by purely molecular arguments-the validity of the ansatz j(v)=(v(1)-v(2))j(1) relating the diffuse volume flux j(v) to the diffuse mass fluxes j(1)(=-j(2)) of the two species and, jointly, their partial specific volumes v(1),v(2). Confirmation of that relation is based upon the use of linear irreversible thermodynamic principles to embed this ansatz in a broader context, and to subsequently establish the accord thereof with Shchavaliev's solution of the multicomponent Boltzmann equation for dilute gases [M. Sh. Shchavaliev, Fluid Dyn. 9, 96 (1974)]. Moreover, because the terms v(1), v(2), and j(1) appearing on the right-hand side of the ansatz are all conventional continuum fluid-mechanical terms (with j(1) given, for example, by Fick's law for thermodynamically ideal solutions), parity requires that j(v) appearing on the left-hand side of that relation also be a continuum term. Previously, diffuse volume fluxes, whether in mixtures or single-component fluids, were widely believed to be noncontinuum in nature, and hence of interest only to those primarily concerned with transport phenomena in rarefied gases. This demonstration of the continuum nature of bivelocity hydrodynamics suggests that the latter subject should be of general interest to all fluid mechanicians, even those with no special interest in mixtures.

Circumstantial evidence in support of bivelocity hydrodynamic theory for mixtures.

Based upon findings with respect to the viability of the expression j(v)=-rhoD(v)nablav hypothesized to represent the constitutive equation for the diffusive volume flux in ideal binary mixtures (rho=mass density, v=1/rho=specific volume, and D(v)=volume diffusion coefficient), implicit evidence is offered in support of the recently developed theory of bivelocity continuum hydrodynamics for mixtures. Present findings for the case of mixtures add to existing evidence already available for the single-component case, thus supporting the viability of bivelocity hydrodynamic theory in general.

Self-thermophoresis and thermal self-diffusion in liquids and gases.

This paper demonstrates the existence of self-thermophoresis, a phenomenon whereby a virtual thermophoretic force arising from a temperature gradient in a quiescent single-component liquid or gas acts upon an individual molecule of that fluid in much the same manner as a "real" thermophoretic force acts upon a macroscopic, non-Brownian body immersed in that same fluid. In turn, self-thermophoresis acting in concert with Brownian self-diffusion gives rise to the phenomenon of thermal self-diffusion in single-component fluids. The latter furnishes quantitative explanations of both thermophoresis in pure fluids and thermal diffusion in binary mixtures (the latter composed of a dilute solution of a physicochemically inert solute whose molecules are large compared with those of the solvent continuum). Explicitly, the self-thermophoretic theory furnishes a simple expression for both the thermophoretic velocity U of a macroscopic body in a single-component fluid subjected to a temperature gradient ∇T , and the intimately related binary thermal diffusion coefficient D{T} for a two-component colloidal or macromolecular mixture. The predicted expressions U=-D{T}∇T≡-ßD{S}∇T and D{T}=ßD{S} (with ß and D{S} the pure solvent's respective thermal expansion and isothermal self-diffusion coefficients) are each noted to accord reasonably well with experimental data for both liquids and gases. The likely source of systematic deviations of the predicted values of D{T} from these data is discussed. This appears to be the first successful thermodiffusion theory applicable to both liquids and gases, a not insignificant achievement considering that the respective thermal diffusivities and thermophoretic velocities of these two classes of fluids differ by as much as six orders of magnitude.

Dispersion phenomena in helical flow in a concentric annulus.

We examined dispersion phenomena of solutes in helical flow in a concentric annulus through a multiscale approach. The helical flow was developed by the combination of the Poiseuille flow and Couette flow. Here, we present an analytic model that can address the multidimensional Taylor dispersion in the helical flow under a lateral field of thermophoresis (or thermal diffusion) in the gapwise direction. Macroscopic parameters including the average solute velocity and dispersivity were analyzed using relevant microscopic physicochemical properties. The mathematically obtained results were validated by the numerical simulation carried out in this study. The findings show that macrotransport processes are robust and straightforward to handle multidimensional dispersion phenomena of solutes in helical flow. This study is expected to provide a theoretical platform for applications of helical flow such as tube exchangers, oil drilling, and multidimensional field flow fractionations (e.g., helical flow field flow fractionation).

Multiscale analysis of thermal field flow fractionation through macrotransport approach.

We introduce the general theory of macrotransport processes to analyze thermal field flow fractionation (ThFFF). Multiscale analysis is carried out by adopting local and total moments. It is shown that the scheme of macrotransport processes is easier to apply and mathematically straightforward than exiting microscopic methods. The mean solute velocity and dispersivity associated with the retention time and standard deviation of a fractogram are calculated considering the temperature dependence of viscosity for ThFFF. A Gaussian distribution function is fitted to the fractogram measured experimentally and then the Soret numbers are calculated by using the retention time and standard deviation.

Elementary kinematical model of thermal diffusion in liquids and gases.

An elementary hydrodynamic and Brownian motion model of the thermal diffusivity D(T) of a restricted class of binary liquid mixtures, previously proposed by the author, is given a more transparent derivation than originally, exposing thereby the strictly kinematic-hydrodynamic nature of an important class of thermodiffusion separation phenomena. Moreover, it is argued that the solvent's thermometric diffusivity alpha appearing in that theory as one of the two fundamental parameters governing D(T) should be replaced by the solvent's (isothermal) self-diffusivity D(S). In addition, a corrective multiplier of O(1) is inserted to reflect the general physicochemical noninertness of the solute relative to the solvent, thus enhancing the applicability of the resulting formula D(T)=lambdaD(S)beta to "nonideal" solutions. Here, beta is the solvent's thermal expansivity and lambda is a term of O(1), insensitive to the physicochemical nature of the solute (thus rendering D(T) primarily dependent upon only the properties of the solvent). This formula is, on the basis of its derivation, presumably valid only under certain idealized, albeit well-defined, circumstances. This occurs when the solute molecules are: (i) large compared with those of the solvent; and (ii) present only in small proportions relative to those of the solvent. When the solute is physicochemically inert, it is expected that lambda=1. When these conditions are met, the resulting thermal diffusivity of the mixture is, in theory, independent of any and all properties of the solute. Moreover, because beta is algebraically signed, the thermal diffusivity can either by positive or negative, according as the solvent expands or contracts upon being heated. This formula for D(T) is compared with available experimental data for selected binary liquid mixtures. Reasonable agreement is found in almost all circumstances with lambda near unity, the more so the higher the temperature, especially when the solute-solvent mixture properties closely approximate those where agreement would be expected and conversely. Finally, it is pointed out that for the restricted circumstances described, the formula D(T)=lambdaD(S)beta is equally credible for gases. Here, based on gas-kinetic theory, it is possible to furnish the theoretical value of lambda. Overall, while spanning a range of about five orders of magnitude, the D(T) values given by this elementary formula are shown to apply with reasonable accuracy to: (i) liquids (including circumstances for which D(T) is negative) as well as gases; (ii) all combinations of solvents and solutes tested (the latter including, for example, polymer molecules and metallic colloidal particles); and (iii) all sizes of solute molecules, from angstroms to submicron.

Nonisothermal Brownian motion: Thermophoresis as the macroscopic manifestation of thermally biased molecular motion.

A quiescent single-component gravity-free gas subject to a small steady uniform temperature gradient T, despite being at rest, is shown to experience a drift velocity UD=-D* gradient ln T, where D* is the gas's nonisothermal self-diffusion coefficient. D* is identified as being the gas's thermometric diffusivity alpha. The latter differs from the gas's isothermal isotopic self-diffusion coefficient D, albeit only slightly. Two independent derivations are given of this drift velocity formula, one kinematical and the other dynamical, both derivations being strictly macroscopic in nature. Within modest experimental and theoretical uncertainties, this virtual drift velocity UD=-alpha gradient ln T is shown to be constitutively and phenomenologically indistinguishable from the well-known experimental and theoretical formulas for the thermophoretic velocity U of a macroscopic (i.e., non-Brownian) non-heat-conducting particle moving under the influence of a uniform temperature gradient through an otherwise quiescent single-component rarefied gas continuum at small Knudsen numbers. Coupled with the size independence of the particle's thermophoretic velocity, the empirically observed equality, U=UD, leads naturally to the hypothesis that these two velocities, the former real and the latter virtual, are, in fact, simply manifestations of the same underlying molecular phenomenon, namely the gas's Brownian movement, albeit biased by the temperature gradient. This purely hydrodynamic continuum-mechanical equality is confirmed by theoretical calculations effected at the kinetic-molecular level on the basis of an existing solution of the Boltzmann equation for a quasi-Lorentzian gas, modulo small uncertainties pertaining to the choice of collision model. Explicitly, this asymptotically valid molecular model allows the virtual drift velocity UD of the light gas and the thermophoretic velocity U of the massive, effectively non-Brownian, particle, now regarded as the tracer particle of the light gas's drift velocity, to each be identified with the Chapman-Enskog "thermal diffusion velocity" of the quasi-Lorentzian gas, here designated by the symbol UM/M, as calculated by de la Mora and Mercer. It is further pointed out that, modulo the collective uncertainties cited above, the common velocities UD,U, and UM/M are identical to the single-component gas's diffuse volume current jv, the latter representing yet another, independent, strictly continuum-mechanical concept. Finally, comments are offered on the extension of the single-component drift velocity notion to liquids, and its application towards rationalizing Soret thermal-diffusion separation phenomena in quasi-Lorentzian liquid-phase binary mixtures composed of disparately sized solute and solvent molecules, with the massive Brownian solute molecules (e.g., colloidal particles) present in disproportionately small amounts relative to that of the solvent.

Is the tracer velocity of a fluid continuum equal to its mass velocity?

Owing to its size independence in the so-called near-continuum vanishingly small Knudsen number regime (Kn<<1) , thermophoretic particle motion occurring in an otherwise quiescent gas under the influence of a temperature gradient is here interpreted as representing the motion of a tracer, namely, an effectively point-size test particle monitoring the local velocity of the undisturbed, particle-free, compressible gas continuum through space. "Compressibility" refers here not to the usual effect of pressure on the gas's mass density rho but rather to the effect thereon of temperature. Our unorthodox continuum interpretation of thermophoresis differs from the usual one, which regards the existence of thermophoretic forces in gases as a strictly noncontinuum phenomenon, involving thermal stress-induced Maxwell slip ("thermal creep") of the gas's mass velocity vm at the surface of the particle, with vm denoting the velocity appearing in the continuity equation expressing the law of conservation of mass. Explicitly, instead of regarding the thermally animated particle as moving through the gas, we regard the particle (in its hypothesized role as a tracer of the undisturbed, particle-free, fluid motion) as moving with the gas, through space; that is, the particle is viewed as simply being entrained in the flowing gas, which, as a result of an externally applied temperature gradient, was already in motion prior to the tracer's introduction into the fluid--albeit not mass motion (which is, in fact, identically zero) but rather volume motion. This tracer-particle interpretation of experimental thermophoretic particle velocity measurements raises fundamental issues in regard to the universally accepted Newtonian rheological law constitutively specifying the viscous or deviatoric stress T as being proportional to the (symmetrized, traceless) fluid velocity gradient inverted Deltav , with v identified as being the fluid's mass velocity vm . Rather, it is argued in the case of compressible fluids, including liquids, that v should, instead, be chosen as the fluid's volume flux density or current density nv , the latter being formally equivalent to the fluid's volume velocity vv , which differs from vm except in the case of incompressible fluids. Apart from this strictly constitutive issue in regard to T , it is further argued that the fluid's tracer or Lagrangian velocity vl:=(deltax/deltat) (x0) along the fluid's spatiotemporal trajectory x=x (x0,t) is equal to vv, rather than to vm. This too is contrary to the heretofore unquestioned supposition that the conceptually distinct fluid velocities vl and vm are not only equal but are, in fact, synonymous. To the extent that vl not equal vm in the nonisothermal fluid case, an optical dye- or photochromic-type experiment (each of the latter two experiments presumably serving to measure vm) will record a different velocity than would a comparable tracer particle velocity measurement, one that measures vl .

Separation mechanisms underlying vector chromatography in microlithographic arrays.

Micropatterned chips possessing an asymmetric, spatially periodic array of obstacles enable the vector (directional) chromatographic separation of charged particles animated by an external electric field. We apply a network theory to analyze the chip-scale (L-scale) transport of finite-size Brownian particles in such devices and identify those factors that break the symmetry of the chip-scale particle mobility tensor, most importantly the hydrodynamic wall effects between the particles and the obstacle surfaces. Our analysis contrasts with prevailing separation theories, which are limited to effectively point-size particles, for which wall effects are negligible. These theories require a biasing of obstacle-scale (l-scale; l<

Body versus surface forces in continuum mechanics: is the Maxwell stress tensor a physically objective Cauchy stress?

The Maxwell stress tensor (MST) T(M) plays an important role in the dynamics of continua interacting with external fields, as in the commercially and scientifically important case of "ferrofluids." As a conceptual entity in quasistatic systems, the MST derives from the definition f(M)def=inverted Delta x T(M), where f(M)(x) is a physically objective volumetric external body-force density field at a point x of a continuum, derived from the solution of the pertinent governing equations. Beginning with the fact that T(M) is not uniquely defined via the preceding relationship from knowledge of f(M), we point out in this paper that the interpretation of T(M) as being a physical stress is not only conceptually incorrect, but that in commonly occuring situations this interpretation will result in incorrect predictions of the physical response of the system. In short, by elementary examples, this paper emphasizes the need to maintain the classical physical distinction between the notions of body forces f and stresses T. These examples include calculations of the torque on bodies, the work required to deform a fluid continuum, and the rate of interchange of energy between mechanical and other modes.