Surfactant adsorption at the salt/water interface: comparing the conformation and interfacial water structure for selected surfactants

We report in situ spectroscopic measurements monitoring the adsorption of a series of carboxylate surfactants onto the surface of the semisoluble, ionic solid fluorite (CaF2). We employ the surface-specific technique, vibrational sum-frequency spectroscopy (VSFS), to examine the effect that surfactant adsorption has on the bonding interactions and orientation of interfacial water molecules through the alteration of the electric properties in the interfacial region. In addition, we report on the chain length and headgroup dependence of the formation of hydrophobic self-assembled monolayers on the surface of the solid phase. Differences in chain length and headgroup functionality lead to large changes in the adsorption behavior and structuring of the monolayers formed and the interactions of interfacial water molecules with these monolayers. Fundamental studies such as these are essential for understanding the mechanisms involved in the surfactant adsorption process, information that is important for industrially relevant processes such as mineral ore flotation, waste processing, and petroleum recovery.     

Dynamics of surfactant sorption at the air/water interface: continuous-flow tensiometry

Dynamic interfacial tensiometry, gauged by axisymmetric drop shape analysis of static drops or bubbles, provides useful information on surfactant adsorption kinetics. However, the traditional pendant-drop methodology is not readily amenable to the study of desorption kinetics. Thus, the question of sorption reversibility is difficult to assess by this technique. We extend classical pendant/sessile drop dynamic tensiometry by immersing a sessile bubble in a continuously mixed optical cell. Ideal-mixed conditions are established by stirring and by constant flow through the cell. Aqueous surface-active-agent solutions are either supplied to the cell (loading) or removed from the cell by flushing with water (washout), thereby allowing study of both adsorption and desorption kinetics. Well-mixed conditions and elimination of any mass transfer resistance permit direct identification of sorption kinetic barriers to and from the external aqueous phase with time constants longer than the optical-cell residence time. The monodisperse nonionic surfactant ethoxy dodecyl alcohol (C(12)E(5)), along with cationic cetyltrimethyl ammonium bromide (CTAB) in the presence of added salt, adsorbs and desorbs instantaneously at the air/water interface. In these cases, the experimentally observed dynamic-tension curves follow the local-equilibrium model precisely for both loading and washout. Accordingly, these surfactants below their critical micelle concentrations (CMC) exhibit no detectable sorption-activation barriers on time scales of order a min. However, the sorption dynamics of dilute CTAB in the absence of electrolyte is markedly different from that in the presence of KBr. Here CTAB desorption occurs at local equilibrium, but the adsorption rate is kinetically limited, most likely due to an electrostatic barrier arising as the charged surfactant accumulates at the interface. The commercial, polydisperse nonionic surfactant ethoxy nonylphenol (NP9) loads in good agreement with local-equilibrium theory but shows deviation from the theoretical washout curve, presumably due to slow desorption of solubilized but otherwise water insoluble components. The polymeric nonionic triblock copolymer Pluronic exhibits almost complete irreversible adsorption at the air/water interface over a molecular-weight range from 3 to 14 kDa. Similar irreversible dynamic behavior is observed for adsorption/desorption of the protein bovine serum albumin (BSA) from dilute aqueous solutions at the air/water interface. The new continuous-flow tensiometer (CFT) is a simple, yet powerful, tool to investigate sorption dynamics at fluid/fluid interfaces, especially for larger molecular weight surface-active agents that exhibit significant hindrance to desorption.     

Adsorption of organosulfur species at aqueous surfaces: molecular bonding and orientation

Four sulfur-containing compounds important to tropospheric chemistry have been examined at the vapor/H2O and vapor/D2O interfaces. These adsorbates, DMS, DMSO, DMSO2, and DMSO3, were studied by surface tension and vibrational sum-frequency spectroscopy (VSFS). Each adsorbate is surface active and each orients with the hydrophobic methyl groups pointed out of the plane of the interface. Their influence on the interfacial water structure is adsorbate dependent. Strong and weak interactions with surface water are observed as well as reorientation of subsurface water molecules, resulting in an increase in interfacial thickness.     

Dynamical and rheological properties of fluorinated surfactant films adsorbed at the pressurized CO2-H2O interface

The dynamics of adsorption, interfacial tension, and rheological properties of two phosphocholine-derived partially fluorinated surfactants FnHmPC, designed to compensate for the weak CO(2)-surfactant tail interactions, were determined at the pressurized CO(2)-H(2)O interface. The two surfactants differ only by the length of the hydrocarbon spacer (5 CH(2) in F8H5PC and 11 CH(2) in F8H11PC) located between the terminal perfluoroalkyl chain and the polar head. The length of this spacer was found to have a critical impact on the adsorption kinetics and elasticity of the interfacial surfactant film. F8H5PC is soluble in both water and CO(2) phases and presents several distinct successive interfacial behaviors when bulk water concentration (C(W)) increases and displays a nonclassical isotherm shape. The isotherms of F8H5PC are similar for the three CO(2) pressures investigated and comprise four regimes. In the first regime, at low C(W), the interfacial tension is controlled by the organization that occurs between H(2)O and CO(2). The second regime corresponds to the adsorption of the surfactant as a monolayer until the CO(2) phase is saturated with F8H5PC, resulting in a first inflection point. In this regime, F8H5PC molecules reach maximal compaction and display the highest apparent interfacial elasticity. In the third regime, a second inflection is observed that corresponds to the critical micelle concentration of the surfactant in water. At the highest concentrations (fourth regime), the interfacial films are purely viscous and highly flexible, suggesting the capacity for this surfactant to produce water-in-CO(2) microemulsion. In this regime, surfactant adsorption is very fast and equilibrium is reached in less than 100 s. The behavior of F8H11PC is drastically different: it forms micelles only in the water phase, resulting in a classical Gibbs interface. This surfactant decreases the interfacial tension down to 1 mN/m and forms a strongly elastic interface. As this surfactant forms a very cohesive interface, it should be suitable for formulating stable water-in-CO(2) emulsions. The finding that the length of the hydrocarbon spacer in partially fluorinated surfactants can drastically influence film properties at the CO(2)-H(2)O interface should help control the formation of microemulsions versus emulsions and help elaborate a rationale for the design of surfactants specifically adapted to pressurized CO(2).     

Kinetic study of adsorption of some biocompounds at the oil/water interface

The adsorption kinetics of some local anesthetics, like dibucaine and tetracaine, and of stearic acid from bulk solutions at the oil/water interface was studied by using the pendent drop and ring methods. The anesthetics were dissolved in aqueous solutions (pH 2), and the fatty acid was dissolved in benzene, each biocompound at several different concentrations in bulk solutions. Kinetic equations for Langmuir mechanism of adsorption at oil/water interface were tested. The kinetic analysis shows that Langmuir kinetic approach describes the dynamic interfacial pressures within the limits of the experimental errors over a wide range of time and for different surfactant concentrations in bulk solutions. It is also concluded that this approach allows the calculation of the ratio of the adsorption and desorption rate constants of these biocompounds at the oil/water interface. Obtained results are in substantial agreement with earlier reported data for the surfactant adsorption as, well as with their molecular structure.     

Chemical oscillation with periodic adsorption and desorption of surfactant ions at a water/nitrobenzene interface.

Chemical oscillations with periodic adsorption and desorption of surfactant ions, alkyl sulfate ions, at a water/nitrobenzene interface have been investigated. The interfacial tension was measured with a quasi elastic laser scattering (QELS) method and the interfacial electrical potential was obtained. We found that this oscillation consists of a series of abrupt adsorptions of ions, followed by a gradual desorption. In addition, we observed that each abrupt adsorption was always accompanied by a small waving motion of the liquid interface. From the analysis of the video images of the liquid interface or bulk phase, we could conclude that each abrupt adsorption is caused by nonlinear amplification of mass transfer of ions from the bulk phase to the liquid interface by a Marangoni convection, which was generated due to local adsorption of the surfactant ions at the liquid interface that resulted in the heterogeneity of the interfacial tension. In the present paper, we describe the mechanism of the chemical oscillation in terms of the hydrodynamic effect on the ion adsorption processes, and we also show the interfacial chemical reaction with ion exchange during the ion desorption process.     

Dynamics of protein and mixed protein/surfactant adsorption layers at the water/fluid interface

The adsorption behaviour of proteins and systems mixed with surfactants of different nature is described. In the absence of surfactants the proteins mainly adsorb in a diffusion controlled manner. Due to lack of quantitative models the experimental results are discussed partly qualitatively. There are different types of interaction between proteins and surfactant molecules. These interactions lead to protein/surfactant complexes the surface activity and conformation of which are different from those of the pure protein. Complexes formed with ionic surfactants via electrostatic interaction have usually a higher surface activity, which becomes evident from the more than additive surface pressure increase. The presence of only small amounts of ionic surfactants can significantly modify the structure of adsorbed proteins. With increasing amounts of ionic surfactants, however, an opposite effect is reached as due to hydrophobic interaction and the complexes become less surface active and can be displaced from the interface due to competitive adsorption. In the presence of non-ionic surfactants the adsorption layer is mainly formed by competitive adsorption between the compounds and the only interaction is of hydrophobic nature. Such complexes are typically less surface active than the pure protein. From a certain surfactant concentration of the interface is covered almost exclusively by the non-ionic surfactant. Mixed layers of proteins and lipids formed by penetration at the water/air or by competitive adsorption at the water/chloroform interface are formed such that at a certain pressure the components start to separate. Using Brewster angle microscopy in penetration experiments of proteins into lipid monolayers this interfacial separation can be visualised. A brief comparison of the protein adsorption at the water/air and water/n-tetradecane shows that the adsorbed amount at the water/oil interface is much stronger and the change in interfacial tension much larger than at the water/air interface. Also some experimental data on the dilational elasticity of proteins at both interfaces measured by a transient relaxation technique are discussed on the basis of the derived thermodynamic model. As a fast developing field of application the use of surface tensiometry and rheometry of mixed protein/surfactant mixed layers is demonstrated as a new tool in the diagnostics of various diseases and for monitoring the progress of therapies.     

Adsorption of CETP on monolayers formed from HDL extracted lipids

To obtain information on the interactions between CETP and HDL3 lipoproteins, we have studied (by surface tension measurements) the adsorption of the CETP at the air–water interface and at the interface between the water and monolayers formed by spreading of lipids extracted from HDL3. We have compared the interfacial behavior of CETP and ApoA-1 (the constitutive protein of HDL3); and the influence of monolayers composition and pressure on the kinetics of the CETP adsorption. The results obtained show that CETP was more expanded than the ApoA-1 which adsorbed more strongly at the air–water interface. CETP adsorbs more and quickly at the lipid interface that at the air–interface, specially for 20% fraction of cholesterol in the monolayer. Our results show that the adsorption of the CETP at the HDL3 surface lipids are strongly dependent of the composition of the monolayer and that the exclusion pressure of CETP varied from 31 to 33.7 mN m⁻¹ with the addition of cholesterol. Finally, the kinetics of the adsorption at water–lipid interface exhibited two steps (quick increase followed by slow decrease of the excess surface pressure) which should indicate a penetration into monolayer followed by a partial desorption of phospholipids with or without cholesterol corresponding to a proteolipid association.     

Mass transfer model of triethylamine across the n-decane/water interface derived from dynamic interfacial tension experiments

This publication presents a detailed experimental and theoretical study of mass transfer of triethylamine (TEA) across the n-decane/water interface. In preliminary investigations, the partition of TEA between n-decane and water is determined. Based on the experimental finding that the dissociation of TEA takes place in the aqueous and in the organic phase, we assume that the interfacial mass transfer is mainly affected by adsorption and desorption of ionized TEA molecules at the liquid/liquid interface. Due to the amphiphilic structure of the dissociated TEA molecules, a dynamic interfacial tension measurement technique can be used to experimentally determine the interfacial mass transport. A model-based approach, which accounts for diffusive mass transport in the finite liquid bulk phases and for adsorption and desorption of ionized TEA molecules at the interface, is employed to analyze the experimental data. In the equilibrium state, the interfacial tension of dissociated TEA at the n-decane/water interface can be adequately described by the Langmuir isotherm. The comparison between the theoretical and the experimental dynamic interfacial tension data reveals that an additional activation energy barrier for adsorption and desorption at the interface has to be regarded to accurately describe the mass transport of TEA from the n-decane phase into the aqueous phase. Corresponding adsorption rate constants can be obtained by fitting the theoretical predictions to the experimental data. Interfacial tension measurements of mass transfer from the aqueous into the organic phase are characterized by interfacial instabilities caused by Marangoni convection, which result in an enhancement of the transfer rate across the interface.     

Specific ion effects on interfacial water structure near macromolecules

We investigated specific ion effects on interfacial water structure next to macromolecules with vibrational sum frequency spectroscopy (VSFS). Poly-(N-isopropylacrylamide) was adsorbed at the air/water interface for this purpose. It was found that the presence of salt in the subphase could induce the reorganization of water adjacent to the macromolecule and that the changes depended greatly on the specific identity and concentration of the salt employed. Ranked by their propensity to orient interfacial water molecules, sodium salts could be placed in the following order: NaSCN > NaClO4 > NaI > NaNO3 approximately NaBr > NaCl > pure water approximately NaF approximately Na2SO4. This ordering is a Hofmeister series. On the other hand, varying the identity of the cation exhibited virtually no effect. We also showed that the oscillator strength in the OH stretch region was linearly related to changes in the surface potential caused by anion adsorption. This fact allowed binding isotherms to be abstracted from the VSFS data. Such results offer direct evidence that interfacial water structure can be predominantly the consequence of macromolecule-ion interactions.     

Interfacial Studies of the Formation of Microemulsions of Water in Carbon Dioxide with Fluorinated Surfactants

Measurements of the interfacial tension, γ, for water-CO₂-perfiuoropoly ether (PFPE) ionic surfactant systems are utilized to understand the surfactant affinity for the various phases and adsorption at the interface. A marked decrease in γ with salinity is observed as salt screens electrostatic repulsion and induces microemulsion formation, as confirmed with dynamic light scattering. In several cases, the interfacial tension goes through an unusual maximum with salinity, which is explained in terms of competition between surfactant affinity for the various phases and microemulsion formation. Fundamental studies of interfacial properties provide important insight for designing surfactants and experimental conditions to achieve the desired properties of water/CO² microemulsions and emulsions.     

Syntheses and properties of novel non-ionic fluorinated multichains “star-like” surfactants

A series of star-like nonionic surfactants (with two hydrophobic and two hydrophilic chains) with different lengths of hydrophilic and hydrophobic arms were synthesised on the basis of pyromellitic acid dianhydride. The hydrophilic arms were formed by polyoxyethylene and hydrophobic ones either by perfluoro- or by alkyl chains. The adsorption monolayers (Gibbs monolayers) were studied by surface pressure (π) measurements as a function of time for different surfactant concentrations. For the spread monolayers (Langmuir monolayers), the measurements of the surface pressure (π) versus the molecular area (A) as well as the relaxation measurements of the area (A) as a function of time at constant surface pressure were performed. The comparison between the characteristic parameters of two types of monolayers was made in order to understand the effect of the preparation conditions on the structure of these monolayers.It was found that decreasing the fluoroalkyl chain length induced a systematical decrease in the stability of Langmuir monolayers, which is manifested as the Marangoni-Gibbs viscoelasticity of the monolayers. For the surfactants, which have a large number of oxyethylene groups, adsorption at the air/water interface from the bulk solution required extremely long times to reach equilibrium due to the diffusion from the solution and to the conformational rearrangements at the interface. The observation of a hysteresis in the compression/decompression curves for these compounds is explained by the presence of the residual organic solvent molecules absorbed by oxyethylenic chains. A novel model describing the kinetics of desorption or rearrangement of molecules during the lateral compression was suggested, allowing the estimation of both characteristic time of this process and areas per molecule at the equilibrium from the relaxation curves A(t).     

Some aspects of stability of multiple emulsions in personal cleansing systems

The two dominant factors that were found to affect the stability of multiple emulsions in high HLB surfactant systems are the osmotic pressure imbalance between the internal aqueous phase and the external aqueous phase, and the adsorption/desorption characteristics of the emulsifier/surfactant film at the oil/water interface. Synergistic interaction between the low HLB emulsifier and the high HLB surfactant that produces very low interfacial tension of the order of 10(-2) mN/m at the oil/water interface was found to occur in some of the systems investigated. Long term stability was observed in multiple emulsion containing these systems. However, no synergy was observed in systems in which either the oil or the emulsifier, or both, contained unsaturated chains. In fact, desorption of the adsorbed surfactant film was observed in systems containing unsaturated chains. The observed desorption from the interface of the emulsifier in these systems was attributed mainly to the inability of the unsaturated chains to form a close packed, condensed interfacial film. Presence of closely packed, condensed interfacial film is necessary to prevent solubilization of the adsorbed low HLB emulsifier by the high HLB surfactant. Multiple emulsions prepared using systems containing unsaturated hydrocarbons were highly unstable.     

界面扩张流变法研究C_(12)mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C12-(CH2)2-C12·2Br(Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C12mim Br)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等,探讨了C12mim Br对C12mim Br/Gemini12-2-12混合体系界面性质的影响及C12mim Br对Gemini12-2-12界面聚集行为影响的机制.结果表明,随着离子液体表面活性剂的不断引入,体系界面吸附达到平衡所需的时间逐渐缩短,扩张模量和相角明显降低,界面吸附膜由粘弹性膜转变为近似纯弹性膜;同时,界面及其附近的弛豫过程也发生显著变化,慢弛豫过程消失,快弛豫过程占主导地位,且离子液体浓度越高,快弛豫的贡献越大.这些界面性质的变化主要归因于离子液体表面活性剂C12mim Br参与界面形成及两表面活性剂在界面竞争吸附的结果.少量离子液体表面活性剂C12mim Br的加入可以填补疏松的Gemini12-2-12界面上的空位,形成混合界面吸附膜.随着C12mim Br含量的增加,嵌入界面的C12mim Br分子数不断增多,导致界面上相互缠绕的Gemini12-2-12烷基链"解缠",在体相和界面分子扩散交换的过程中"解缠"的Gemini12-2-12分子从界面上解吸回到体相,与此同时,C12mim Br分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子,最终界面几乎完全被C12mim Br分子所占据.     

Adsorption/aggregation of surfactants and their mixtures at solid-liquid interfaces

Adsorption of surfactants and polymers at solid-liquid interfaces is used widely to modify interfacial properties in a variety of industrial processes such as flotation, ceramic processing, flocculation/dispersion, personal care product formulation and enhanced oil recovery. The behavior of surfactants and polymers at interfaces is determined by a number of forces, including electrostatic attraction, covalent bonding, hydrogen bonding, hydrophobic bonding, and solvation and desolvation of various species. The extent and type of the forces involved varies depending on the adsorbate and the adsorbent, and also the composition and other characteristics of the solvent and dissolved components in it. The influence of such forces on the adsorption behavior is reviewed here from a thermodynamics point of view. The experimental results from microcalorimetric and spectroscopic studies of adsorbed layers of different surfactant and polymer systems at solid-liquid interfaces are also presented. Calorimetric data from the adsorption of an anionic surfactant, sodium octylbenzenesulfonate, and a non-ionic surfactant, dodecyloxyheptaethoxyethylalcohol, and their mixtures on alumina, yielded important thermodynamic information. It was found that the adsorption of anionic surfactants alone on alumina was initially highly exothermic due to the electrostatic interaction with the substrate. Further adsorption leading to a solloid (hemimicelle) formation is proposed to be mainly an entropy-driven process. The entropy effect was found to be more pronounced for the adsorption of anionic-non-ionic surfactant mixtures than for the anionic surfactant alone. Fluorescence studies using a pyrene probe on an adsorbed surfactant and polymer layers, along with electron spin resonance (ESR) spectroscopy, reveal the role of surface aggregation and the conformation of the adsorbed molecules in controlling the dispersion and wettability of the system.     

Application of Statistical Rate Theory of Interfacial Transport to Study Solid Surface Heterogeneity from Controlled-rate Thermal Desorption

Controlled-rate thermodesorption (CRTD) spectra are obtained by adjusting the heating rate in such a way that the rate of desorption can be constant. A quantitative analysis of the obtained spectra is presented, based on application of the statistical rate theory of interfacial transport (SRTIT) to describe both adsorption and desorption kinetics. The SRTIT approach relates the rates of adsorption and desorption to the chemical potentials of the adsorbate in the gaseous and in the adsorbed phases. This quantitative analysis of the CRTD spectra yields the condensation approximation for the actual adsorption energy distribution. For the purpose of illustration, an analysis is made of water desorption from a synthetic apatite mineral under CRTD and classical TPD conditions. The influence of the adsorption and desorption rates is also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polyelectrolyte/surfactant mixtures in the bulk and at water/oil interfaces

Stabilization of emulsions by mixed polyelectrolyte/surfactant systems is a prominent example for the application in modern technologies. The formation of complexes between the polymers and the surfactants depends on the type of surfactant (ionic, non-ionic) and the mixing ratio. The surface activity (hydrophilic–lipophilic balance) of the resulting complexes is an important quantity for its efficiency in stabilizing emulsions. The interfacial adsorption properties observed at liquid/oil interfaces are more or less equivalent to those observed at the aqueous solution/air interface, however, the corresponding interfacial dilational and shear rheology parameters differ quite significantly. The interfacial properties are directly linked to bulk properties, which support the picture for the complex formation of polyelectrolyte/surfactant mixtures, which is the result of electrostatic and hydrophobic interactions. For long alkyl chain surfactants the interfacial behavior is strongly influenced by hydrophobic interactions while the complex formation with short chain surfactants is mainly governed by electrostatic interactions.     

Study of surfactant-polymer system containing a novel ternary sulfonated polyacrylamide on the oil-water interface properties

A novel ternary sulfonated polyacrylamide was synthesized using 2,2′-azobis[2- methylpropionamidine] dihydrochloride and redox initiation system as initiator, respectively. The competitive adsorption of the ternary sulfonated polyacrylamide (TSPAM) and sodium dodecyl benzene sulfonate (SDBS) on the oil-water interface was investigated by equilibrium interfacial tension, interfacial viscoelasticity, zeta potendial and interfacial film strength. The SDBS molecules in the surfactant-polymer (SP) system preferentially adsorb on the oil-water interface due to the amphiphilic structure of the SDBS molecules. Electrostatic force between the charged groups of the polyacrylamide and the head groups of surfactant adsorbed on the interface in the SP system leads to the formation of the complex interface film, which is helpful to enhance the stability of the oil-water interface. The ternary sulfonated polyacrylamide (TSPAM) has a similar influence on the other interface properties with SDBS except the interfacial tension. The interfacial tension decreases and then increases with increasing of the TSPAM concentration due to the competitive adsorption of the TSPAM molecules and the SDBS molecules on the oil-water interface. Moreover, TSPAM has the more influence on the stability of oil-water interface than partially hydrolyzed polyacrylamide (HPAM) in the SP system, and the addition of TSPAM is better to improve the stability of emulsion in the SP flooding.     

Marangoni flow of Ag nanoparticles from the fluid-fluid interface

Fluid flow is observed when a volume of passivated Ag nanoparticles suspended in chloroform is mixed with a water/ethanol (v/v) mixture containing acidified 11-mercaptoundecanoic acid. Following mechanical agitation, Ag nanoparticles embedded in a film are driven from the organic-aqueous interface. A reddish-brown colored film, verified by transmission electron microscopy to contain uniformly dispersed Ag nanoparticles, is observed to spontaneously climb the interior surface of an ordinary, laboratory glass vial. This phenomenon is recorded by a digital video recorder, and a measurement of the distance traveled by the film front versus time is extracted. Surface (interfacial) tension gradients due to surfactant concentration, temperature, and electrostatic potential across immiscible fluids are known to drive interface motion; this well-known phenomenon is termed Marangoni flow or the Marangoni effect. Experimental results are presented that show the observed mass transfer is dependent on an acid surfactant concentration and on the volume fraction of water in the aqueous phase, consistent with fluid flow induced by interfacial tension gradients. In addition, an effective desorption rate constant for the Marangoni flow is measured in the range of approximately 0.01 to approximately 1 s(-1) from a fit to the relative film front distance traveled versus time data. The fit is based on a time-dependent expression for the surface (interface) excess for desorption kinetics. Such flow suggests that purposeful creation of interfacial tension gradients may aid in the transfer of 2- and 3-dimensional assemblies, made with nanostructures at the liquid-liquid interface, to solid surfaces.