Probe Liquids Research Articles

Superhydrophilic‐underwater superoleophobic polyvinyl alcohol membranes for oily water treatment

AbstractPolyvinyl alcohol (PVA) and potato starch‐based porous hydrogels have been fabricated and studied for their wettability. The starting material was crosslinked by glutaraldehyde performed via co‐polymerization reaction at room temperature and low temperature (freeze–thaw). The gels were characterized by Fourier transform infrared (FT‐IR), field emission scanning electron microscope (FE‐SEM), thermogravimetric (TG), and powder X‐ray diffraction (PXRD) analysis. The wetting studies of the gels were evaluated at ambient and submerged conditions by considering both oil and water drops as probe liquids. The gels tend to absorb oil and water in air, however, water‐wet gels demonstrated a very high oil contact angle (>150°). The gels demonstrated superoleophobicity, and the underwater oil CA >172° as the concentration (wt%) of PVA was increased in the gels. Overall, the freeze–thaw gels demonstrated higher underwater oil CA, however, both (room temperature and freeze–thaw fabricated) gels demonstrated similar affinity for under‐oil–water absorption and separation. The hydrogel can retain water easily and thus remove water (even dye dissolved in water) with high separation efficiency and recyclability.

A review of ion scattering spectroscopy studies at liquid interfaces with noble gas ion projectiles

Ion scattering spectroscopy (ISS) is an analytical tool that provides direct structural, topographical, and atomic compositional information at interfaces when ions are used as projectiles. Since its development in 1967, ISS is commonly used to obtain quantitative information about solid interfaces. Over the last couple of decades, ISS has emerged as an important technique to probe liquid interfaces and their studies employing ISS has become not uncommon, more so with Neutral impact collision ion scattering spectroscopy (NICISS). Therefore, here the principle of ISS with a particular focus on NICISS and its data evaluation are summarised while reviewing some important studies at vapor-liquid interfaces that provide direct information for molecular orientation of liquids (including ionic liquids), composition and distribution of atoms (or solutes) and charges as a function of depth to gain vast variety of thermodynamical information. Employing ISS such information can be achieved with high depth resolution of ∼1–2 Å (depending on the nature of the experiment). These examples highlight the significance of ISS and show potential for its application for studies related to specific ion effects, atmospheric reaction in aerosol and sea water droplets, and even determining the fate of environmental pollutants like heavy metal ions and per-fluoroalkyl substances (PFAS). Furthermore, some limitations of ISS are also discussed relating to investigation of high-vapor pressure liquids and probing buried interfaces like liquid-liquid interfaces while presenting progresses made in probing solid-liquid interfaces.

Unraveling the NH3-SCR-DeNOx Mechanism of Cu-SSZ-13 Variants by Spectroscopic and Transient Techniques.

Commercial SSZ-13 zeolite with different n(Si)/n(Al) ratios and from different suppliers were subjected to a post-synthetic treatment in order to create mesopores of up to 15 nm. Furthermore, the materials were modified with copper ions and thoroughly physico-chemically characterized. The modified textural properties varied the nature of copper species, and thus, activity in the selective catalytic reduction of NOx with ammonia (NH3-SCR-DeNOx). Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) studies with hexane as probe liquid revealed improved intracrystalline diffusion for some Cu-containing SSZ-13 materials. The NH3-SCR-DeNOx pathways are verified via in situ DR UV-Vis, in situ FT-IR and EPR, temperature-programmed studies as well as SSITKA studies that provide a mechanistic understanding of the reaction. Kinetic modelling results demonstrate the highest NH3-SCR-DeNOx reaction rates and up to 20 % lower energy barriers with n(Si)/n(Al) ratio of 6.5 for all modified forms (i. e., (NH4)Cu-SSZ-13_6.5 and Cu-SSZ-13_6.5_NaOH/0.1) and cause only negligible parasitic ammonia oxidation. The modelling of the stop-flow experiments further demonstrates that the SCR pathway via the HONO surface intermediate is present but barely contributes to the overall NO conversion compared to the dominant path between adsorbed NH3 and NO from the gas phase.

Dispersion Stability of Inorganic Powders Harnessed to Mosaic Surface Ligands via Multifit Hansen Solubility Parameters.

This study assessed the dispersion stability of industrial carbide/oxide powders that have mosaic surfaces comprised of multiple surface ligands. A large number (∼50) of probe liquids were used with an aim to effectively explain the data within the Hansen solubility parameter (HSP) framework. The proposed log-fit method, complemented by multi-HSP analysis featuring harmonic-mean-mixing HSPs, significantly improved the fit to experimental results for various mosaic-surface powders composed of complex surface ligands. X-ray photoelectron spectroscopy and thermal desorption spectroscopy analyses were employed synergistically to decipher the surface ligands of these mosaic-surface powders, which facilitated credible identification and quantification of the surface ligands. These results are in good agreement with the surface ligands and their coverage as determined by the multi-HSP analysis. Consequently, when it comes to characterizing powder surfaces, dispersion stability measurements paired with multi-HSP analysis are superior to conventional XPS and TDS analyses in terms of both topmost surface sensitivity and practicality.

Modeling and prediction of surface free energy of pavement materials based on a single probe liquid using artificial neural network

Surface free energy (SFE) is a vital material property employed for the assessment of various pavement performances such as asphalt-aggregate adhesion, moisture resistance, material compatibility, etc. However, the conventional models for estimating the SFE of materials require the contact angles (CA) of multiple probe liquids (PL) on the material's surface. In addition, the process requires further computational effort to arrive at the SFE components. In an attempt to offer an accurate and quicker alternative method of estimating the SFE of materials with lesser effort, this study has explored the use of artificial neural network (ANN) to predict the SFE of pavement materials. A simple but novel data structuring was employed to predict the SFE using inputs from just a single PL. Variables needed for the successful prediction of SFE components were identified and studied. Sensitivity analysis along with relative importance was used to rank the predicting variables. The Lifshitz-van der Waals (LW) component ANN-model showed the best accuracy (RMSE = 1.652 J/m2, R = 0.984). The base and acid components models showed relatively lower performances, (RMSE = 2.560 J/m2, R = 0.943) and (RMSE = 0.575 J/m2, R = 0.818) respectively. However, the SFE components estimated from the ANN-models yielded a total SFE with very good accuracy (RMSE = 2.049 J/m2, R = 0.982). Further insight into which variables such as substrate-type, CA test method, PL type, etc. facilitate model accuracy was provided.

A Procedure for Rational Probe Liquids Selection to Determine Hansen Solubility Parameters

AbstractHansen Solubility Parameters (HSP), viewed in the context of similarity whenever dispersion is focused, offer valuable insights into the surface characteristics of nanoparticles. However, existing methods for determining HSP via the sedimentation of nanoparticles require multiple probe liquids, resulting in time‐consuming, costly experiments with potential health risks. To address this, we developed a two‐step strategy that enables a systematic selection of liquids. The key element of the approach is to first identify the rough location of the Hansen sphere in the three‐dimensional Hansen space using a well‐chosen set of probe liquids of different polarities and chemical structures. Then, depending on the outcome of the first step, a particular choice of liquids is made for the final HSP determination. Taken together, the introduced procedure reduces the amount of required liquids for experiments from currently more than ten to a maximum of seven chosen based on a well‐defined, coherent methodology. Validation was performed on carbon black, non‐pigmentary nano‐scale titania, silicon/carbon composites, and lanthanum cobaltite particles, i. e., relevant materials that are commonly utilized in fuel cells, batteries, cyclohexene oxidation, catalytic combustion, photocatalysis, and heterogeneous Fenton reactions. The study showcases the potential to save time, costs, and efficiently determine HSP values in a comparable manner.

Comparison of water and benzene as probe liquids in thermoporometry of mesoporous carbons

Water and benzene were compared as probe liquids for thermoporometric characterization of mesoporous carbons. For testing, four different carbonaceous materials were prepared by soft- or hard-templating procedures with mesopore diameters in the range 3–12 nm. In addition, all materials were tested in hydrophobic (pristine, carbonized at 900 °C) and hydrophilic (moderate oxidation by persulphate) form. The results show that both tested liquids express a good linear correlation between heat of melting in pores (measured as DSC peak area) and volume of mesopores. Melting point depression of probe liquid confined in pores related to mesopore size was found out to be steeper for benzene confirming a higher value of Gibbs-Thomson constant of benzene compared to water. Neither heat of melting in pores nor melting point depression were affected by carbon surface oxidation. Contrary, the non-freezing layer (δ layer) of a liquid in pores was considerably wider for most of hydrophilic samples than hydrophobic ones when water was employed, while it stayed nearly constant when benzene was applied. Nevertheless, both tested probe liquids generally enable to obtain similar pore size distributions if appropriate values of δ layers are used. Benzene as a probe liquid in thermoporometry of carbons have some advantages compared to water but only in limited cases. Benzene can be recommended for characterisation of large mesopores and its usage can be beneficial for comparison of analogous samples with different surface chemistry.

The Relevance of Carbon for Energy Transition: Ways to Assess Its Surface Properties and Standardize Their Characterization

Technical carbon blacks (CB) are well-established materials that gain increasing attraction in the context of electrification and transition towards renewable energy sources. Their availability, low price, and favorable properties (e.g., conductivity, specific surface area) make them ideal candidates as additives in batteries or as support material for electrocatalysts, e.g., in fuel cells [1]. However, due to the vast number of producers and manufacturing processes large variations in their properties can be observed making product quality control difficult.To this end, we report on ways and methods to standardize the characterization of CB materials that are specifically designed for fuel cell and battery applications. By applying analytical centrifugation (AC) and combining it with complementary methods (e.g., electrical conductivity measurements, Boehm titration), we identify parameters like particle size, morphology, and surface properties that are influential for the overall value chain in electrode manufacturing. This helps to minimize the effects of material inherent property fluctuations as well as process-related fluctuations on the final electrochemical performance.Four different CBs were investigated, and their various properties were assessed. Our results show that the degree of graphitization and hence the electrical conductivity in a CB can be correlated with the overall surface basicity. Moreover, these properties can be linked with their dispersibility features on the ink formulation level and studied via liquid phase characterization using Hansen Parameters (Fig. 1) [2]. In brief, the higher the basicity of a CB surface is, the better the interaction with non-polar/mildly polar aprotic solvents becomes. This is especially true when oxygen-containing surface functional groups that cause a higher overall polarity of the material are missing.Figure 1: Hansen interaction space (for polar, disperse and hydrogen bonding interactions) showing the location of various solvents that are used as probe liquids for determining the Hansen Similarity Parameters of the respective CBs in 3D space (a) and 2D representations (b-d).To conclude, we were able to identify differences in CB materials by applying AC-based characterization techniques. Those differences can have a huge impact on the overall process chain of electrode production as they are decisive not only in formulation considerations but also in the subsequent processing steps. In the future, we will focus on closing the process chain and try to apply our characterization routines for an efficient identification of decisive process parameters at every stage of production. Additionally, we want to transfer knowledge gained from lab-scale techniques (e.g., sonication methods) to industrially relevant mixing procedures. By this, we will give electrode manufacturers tools at hand for a fast characterization of feed materials to save costly and lengthy adjustments of processes due to quality fluctuations. An accelerated implementation of green energy solutions is sought by this approach.

Thermoporometry of mesoporous carbons: Application of octamethylcyclotetrasiloxane as probe liquid for small mesopores

The mesoporosity of carbons can be determined using traditional methods such as gas physisorption or mercury intrusion, as well as by an alternative technique, thermoporometry (TPM). TPM focuses on determining porosity in the wet state. If water is used as probe liquid, the mesopores larger than 10 nm are hard to evaluate due to the overlapping of pore and bulk melting peaks. To overcome this problem, octamethylcyclotetrasiloxane (OMCTS) is used. Due to the fact that OMCTS undergoes solid-solid phase change in the same temperature range as melting in small mesopores, its use for mesopores below 10 nm is problematic. Thus, the applicability of OMCTS as a probe liquid for TPM characterization of small mesopores was tested in this work. The separation of melting in small pores from solid-solid transition was elaborated by several approaches like changes of heating rate, implementation of prefreezing step, deconvolution of experimental DSC records with the use of basic kinetic equation as underlying functions). It was found that the prefreezing step and a measurement of pure OMCTS under the same conditions as expected for TPM measurement is useful since the solid-solid transition depends on the measurement conditions. The usefulness of the suggested measurement conditions and deconvolution method was successfully demonstrated on carbonaceous samples with exclusively small mesopores (5 nm), as well as carbons containing both small and large mesopores. The results indicate that this approach enables the investigation of the entire mesoporous range and makes OMCTS a more versatile probe liquid for TPM.

Analysis of the general uncertainty propagation and calculation of the systematic uncertainty of the Neumann equation of state for surface free energy determination

The determination of the surface free energy (γSV) of solid materials provides information to explain and understand a wide variety of phenomena in surface science. One of the most widely used methods to determine the value of γSV is the Neumann equation of state (EQS), whose application requires the values of the contact angle (θ) and the surface tension of a probe liquid (γLV). Both parameters are determined experimentally, and their values may be subject to considerable uncertainty. In the present work, the uncertainties of the EQS are analyzed by means of the Taylor series method, using a polynomial adjustment to the EQS previously reported. This analysis allowed us to determine the effects of the θ and γLV uncertainties on γSV values. The γSV of polyoxymethylene (POM) and polytetrafluoroethylene (PTFE) was calculated using the EQS from four probe liquids and taking into account the propagation of the θ and γLV uncertainties. Generally, the comparison of the γSV values calculated from the different probe fluids revealed significant differences. As a solution to this inconsistency in the EQS method, we proposed taking into account a systematic standard uncertainty associated with the method equal to 1.3 mJ/m2. This allowed the differences between the γSV values for the different probe liquids to be non-significant and therefore the method to be consistent.

On the Use of Probe Liquids for Surface Energy Measurements.

To assess the surface energy of solids, normally a set of probe liquids comprising polar and apolar compounds is used. Here we survey the surface tension of some frequently used probe liquids as given in the literature, for which a significant scatter appears to be present, and compare them with experimentally determined values. We discuss the influence of the liquid purity as well as the contact angle between the liquid and the Wilhelmy plate, which is commonly used for surface tension measurements. For hygroscopic polar probe liquids such as dimethyl sulfoxide, ethylene glycol, and formamide, water impurities appear to be of limited importance. Similarly, the amount of halogen impurities is of minor importance for diiodomethane and 1-bromonaphthalene, which decompose under the influence of light. Conversely, the influence of the contact angle for liquids that do not fully wet the plate, such as diiodomethane, is large in many cases, rendering a rather accurate determination of the contact angle necessary. Some discrepancies in the literature are indicated, and brief recommendations for future studies using such liquids are given.

Determination of Hansen Parameters of Nanoparticles: A Comparison of Two Methods Using Titania, Carbon Black, and Silicon/Carbon Composite Materials

AbstractHansen solubility parameters (HSPs), for particles understood as Hansen similarity parameters, can provide valuable information about the surface behavior of nanoparticles. In the past years, several methodologies are developed for scoring and ranking of probe liquids for HSP determination. Two methods available to carry out this determination in a structured way are based on integral extinctions (IE) by Süß et al. and particle size determinations by Anwar et al., respectively. In this study, these two methods of HSP determination are applied on titania, carbon black, and silicon/carbon composites. The differences in scoring and subsequent ranking of a probe liquid list are compared between both methods. Comparable HSPs from both methods are reported as a best‐practice example and additional considerations that need to be considered to properly derive HSPs from the IE‐based method are emphasized.

Hansen Solubility Parameters for Directly Dealing with Surface and Interfacial Phenomena.

To integrate surface and interfacial properties and phenomena into the Hansen solubility parameter (HSP) framework, we propose an equation for estimating both surface tension/energy for liquids and solids as well as interfacial tension/energy. The contact angles of probe liquids on various polymers estimated using the proposed equation based on bulk HSPs (derived from bulk properties such as solubility or swelling, and not on surface properties) are compared with those measured using the sessile drop method. It is found that their correlations are sufficient for predicting wettability in practical use. All the respective tension and energy correlations are reasonably good, confirming the predictive power of the proposed equation for all values of liquid surface tension, solid surface energy, and interfacial tension. The unification of surface and interfacial properties and phenomena with HSPs (derived from bulk properties) enables us to estimate the surface properties from bulk properties and vice versa. The huge database of HSPs is now applicable to not only bulk phenomena but also surface and interfacial phenomena. Furthermore, complex processes or systems composed of multiple constituents and phases can be understood and designed using the modified HSP framework.

A waterfall of possibility: probing liquid flatjets with photoelectron spectroscopy

Method enables study of the electronic structure of molecules at liquid-liquid interfaces and can probe chemical reactions in real time.

Tailoring the Acidity of Liquid Media with Ionizing Radiation: Rethinking the Acid–Base Correlation beyond pH

Advanced in situ techniques based on electrons and X-rays are increasingly used to gain insights into fundamental processes in liquids. However, probing liquid samples with ionizing radiation changes the solution chemistry under observation. In this work, we show that a radiation-induced decrease in pH does not necessarily correlate to an increase in acidity of aqueous solutions. Thus, pH does not capture the acidity under irradiation. Using kinetic modeling of radiation chemistry, we introduce alternative measures of acidity (radiolytic acidity π* and radiolytic ion product KW*), that account for radiation-induced alterations of both H+ and OH- concentration. Moreover, we demonstrate that adding pH-neutral solutes such as LiCl, LiBr, or LiNO3 can trigger a significant change in π*. This provides a huge parameter space to tailor the acidity for in situ experiments involving ionizing radiation, as present in synchrotron facilities or during liquid-phase electron microscopy.

Fluorine-Free Super-Liquid-Repellent Surfaces: Pushing the Limits of PDMS

Methods for fabricating super-liquid-repellent surfaces have typically relied on perfluoroalkyl substances. However, growing concerns about the environmental and health effects of perfluorinated compounds have caused increased interest in fluorine-free alternatives. Polydimethylsiloxane (PDMS) is most promising. In contrast to fluorinated surfaces, PDMS-coated surfaces showed only superhydrophobicity. This raises the question whether the poor liquid repellency is caused by PDMS interacting with the probe liquid or whether it results from inappropriate surface morphology. Here, we demonstrate that a well-designed two-tier structure consisting of silicon dioxide nanoparticles combined with surface-tethered PDMS chains allows super-liquid-repellency toward a range of low surface tension liquids. Drops of water-ethanol solutions with surface tensions as low as 31.0 mN m-1 easily roll and bounce off optimized surface structures. Friction force measurements demonstrate excellent surface homogeneity and easy mobility of drops. Our work shows that fluorine-free super-liquid-repellent surfaces can be achieved using scalable fabrication methods and environmentally friendly surface functionalization.

Polynomial functions for direct calculation of the surface free energy developed from the Neumann equation of state method

The Neumann Equation of State (EQS) allows obtaining the value of the surface free energy of a solid (γSV) from the contact angle (θ) of a probe liquid with known surface tension (γLV). The value of γSV is obtained by numerical methods solving the corresponding EQS. In this work, we analyzed the discrepancies between the values of γSV obtained using the three versions of the EQS reported in the literature. The condition number of the different EQS was used to analyze their sensitivity to the uncertainty in the θ values. Polynomials fit to one of these versions of EQS are proposed to obtain values of γSV directly from contact angles (γSV(θ)) of particular probe liquids. Finally, a general adjusted polynomial is presented to obtain the values of γSV not restricted to a particular probe liquid (γSV(θ,γLV)). Results showed that the three versions of EQS present non-negligible discrepancies, especially at high values of θ. The sensitivity of the EQS to the uncertainty in the values of θ is very similar in the three versions and depends on the probe liquid used (greater sensitivity at higher γLV) and on the value of γSV of the solid (greater sensitivity at lower γSV). The discrepancy of the values obtained by numerical resolution of both the fifth-order fit polynomials and the general fit polynomial was low, no larger than ±0.40 mJ/m2. The polynomials obtained allow the analysis and propagation of the uncertainty of the input variables in the determination of γSV in a simple and fast way.

The implementation of an easy-to-apply NMR cryoporometric instrument for porous materials

Time-domain NMR has been extensively utilised to study various characteristics of fluid-saturated porous,materials for instance their mobility, dynamics, stiffness, viscosity and rigidity features, particularly for solid hydrocarbons, rubbers and other polymers. As a unique time-domain technique available for over 30 years, NMR cryoporometry (NMRC) may be used to obtain pore-size distributions of the measured samples. To accurately control the sample temperature, a Peltier thermo-electrically cooled variable temperature probe has been developed and integrated with a highly compact precision NMR time-domain relaxation spectrometer, therefore providing the community with a high-performance instrument for NMR Cryoporometry. To extend the application of aforementioned high-performance NMRC instrument into more senarios, we designed a series of light-weight, compact and integral models with optional NMR frequencies from 12 MHz up to 23 MHz. The measured sample temperature can be precisely controlled from about −60 °C to +80 °C, with an excellent temperature resolution of 10 mK or better near the probe liquid bulk melting point. Therefore, it offers a fairly wide NMRC pore-size distribution ranging from about 1 nm to 2 μm by using water as the probe liquid in the pores, significantly wider than is possible when applying generic NMR Spectrometers for NMRC. A preliminary example of NMR Cryoporometric measurements on two special cement samples is shown in the paper in which the measured pore scales as well as their repeatability are demonstrated. Furthermore, various nano-materials, such as MOF, zeolite and shale kerogen would be potential materials to study by using these new available NMRC instrument models. We aim to offer this technique as a quantitative and easy-to-apply unitary benck-top tool for an even wider range of porous material.

Carbonate-Terminated Self-Assembled Monolayers for Mimicking Nanoscale Polycarbonate Surfaces

Two carbonate-terminated alkanethiol molecules having different positional isomers of a six-membered cyclic carbonate group, 3-COC12SH and 2-COC12SH, were synthesized and used to generate self-assembled monolayers (SAMs) on gold to serve as mimics of the surfaces of commercially available poly(propylene carbonate) (PPC) and poly(ethylene carbonate) (PEC). The adsorbate molecules were characterized using 1H and 13C nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. The corresponding SAMs on gold were characterized by ellipsometry, contact angle goniometry, polarization-modulation infrared reflection-adsorption spectroscopy, and X-ray photoelectron spectroscopy. The contact angle data showed that the wettabilities of both SAMs were largely similar to each other and to the PEC samples for a wide range of contacting probe liquids (with water correlating particularly well with PEC and both SAMs). As a whole, the wettability data suggest that the carbonate-terminated SAMs can serve as mimics of nanoscale polycarbonate surfaces and can be used to investigate the interfacial properties of polycarbonates without interference from the surface reconstruction.

Surface free energy and roughness of flowable dental composites

Purpose The surface properties like roughness, wettability and surface free energy are important for utility properties of traditional and flowable dental restorative composites, due to their role in plaque formation, discoloration, mechanical wear or adhesion and bonding. The goal of our work was to assess the surface free energy (SFE) and the surface roughness (Ra) of three commercial flowable dental composites: everX Flow (bulk), everX Flow (dentin) and Flow-Art. Methods Surface roughness, contact angle and surface free energy were determined for tested composites. Two surface states (control and roughened) were compared. Roughness was measured with the use of the 3D optical profilometer. The contact angle (CA) was determined through the sessile drop method with the use of four different probing liquids. This enabled to apply two surface free energy approaches (Owens–Wendt (O-W) and van Oss–Chaudhury–Good (LWAB)). Additionally, Zisman’s approach (γC) was used. Results The water contact angle values were similar for Flow-Art (67.56±1.49°) and everX Flow (bulk) (68.94±2.72°) compared to higher value for everX Flow (dentin) (74.39±2.05°). SFE was in the range from 43 to 50 mJ/m^2 for O-W and from 47 to 62 mJ/m2 for LWAB. The γC was from 37 to 45 mJ/m^2. Conclusions Roughening composites’ surface influenced on increasing the CA value. All approaches of surface free energy calculations provide useful data for predicting interactions between flowable composites and dental tissues. Tested composites showed good wetting for initial state of surface after polymerization. These influence on better adhesion of the material to the bonding system during dental restoration.