The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory sums the attractive van der Waals and repulsive electrostatic forces as a function of separation distance to predict the interaction between charged particles immersed in a liquid. In aqueous media, however, non-electrostatic polar (electron acceptor/electron donor or Lewis acid/base) forces between particles with high energy surfaces often are comparable to, or greater than, the components of DLVO theory. By means of contact angle measurements on smooth self-supporting clay films, the values of the polar surface forces (AB) and the van der Waals forces (LW) of hectorite were measured. Determinations of ζ were used to derive the electrostatic forces (EL). Calculations based on the values obtained for the EL, LW, and AB forces show that for smooth spheres with a radius of 1 µm in a ≥ 0.1 M NaCl solution a net attraction exists leading to flocculation. At NaCl concentrations of ≤ 0.01 M, a repulsion energy of about +500 to +1300 kT exists at separation distances ≤ 50 Å, preventing contact between particles, thus ensuring stability of the colloidal suspension. At these concentrations, theory predicts that small clay particles or edges of clay crystals having an effective radius of curvature ≤ 10 Å should be energetic enough to overcome the repulsion barrier which prevents flocculation. Experimentally, for NaCl solution concentrations of ≥ 0.1 M, suspensions of hectorite particles flocculated, whereas at concentrations of ≥ 0.01 M, the suspensions remained stable. These experimental results agree with the predictions made by summing all three forces, but contradict the calculations based on classical DLVO theory.

Contact angles of glycerol and diiodomethane drops were measured on the surface of kaolin pellets covered with different amounts of dodecylamine chloride (DDACl) to as much as one monolayer. For a glycerol drop, the contact angle changed from 25.7° (bare surface) to 45.4° for the surface precoated with 0.125 monolayer of DDACl, but remained nearly constant above this level up to one monolayer. For a diiodomethane drop, the contact angle changed from 28.6° (bare surface) to 58.1° for one DDACl monolayer precoating. Using these contact angles and a modified Young equation, the dispersive and nondispersive components of the surface free energy of DDACl-covered kaolin were calculated. These data showed that in the extreme case (one monolayer) the dispersive component was reduced by the DDACl from ∼36 mJ/m2 (bare surface) to 25.4 mJ/m2, i.e., the value characteristic for paraffin (25.5 mJ/m2); however, the nondispersive component was not reduced to zero. A minimum value (15.83 mJ/m2) was determined for the sample covered with 0.125 DDACl monolayer (calculated), and a slight increase in the nondispersive component was observed for greater coverages. Such a change of the nondispersive component suggests that, at higher coverages, some adsorbed DDACl molecules were oriented with their polar ends off the surface. Based on the values of the γsfd and γsfn, the work of water spreading was calculated. This work was positive for the bare surface (32.8 mJ/m2) and methanol-treated (36.5 mJ/m2) kaolin surface, but negative for 0.125 DDACl monolayer precoating (-31.1 mJ/m2). It remained essentially unchanged for higher coverages. These data mean that bare and methanol-treated kaolinite surfaces were hydrophilic and that DDACl-treated surfaces were hydrophobic.

The influence of adsorbed H+, Na+, K+, Ca2+, Mg2+, Ba2+, and Al3+ ions on the wettability of a kaolinite surface was determined from contact angles, which were measured in kaolinite-water drop-air (saturated water vapor) and kaolinite-diiodomethane drop-air systems. From the results and using a modified Young equation, the dispersion and nondispersion components of the free energy of the kaolinite hydrated surface were determined. The dispersion component of all the tested samples was between 32.8 and 38.9 mJ/m2, but the nondispersion component changed almost linearly from 53 to 95.9 mJ/m2 with the change of the entropy of hydration of the adsorbed ions, except for K+ and Ba2+. The latter ions were exceptions, probably due to their large ionic radii.

Purification of raw bentonites and organo-bentonite preparations is sometimes required for industrial use. Zeta (electrokinetic) potential (ζ), contact angle (wettability/hydrophobicity), and surface free energy (SFE) are important surface characteristics and vary significantly according to the applied surfactant concentration when preparing organo-bentonite. Changes in these characteristics determine the stability, behavior, and efficiency of organo-bentonites in various applications such as adsorption, composite materials, and drug-delivery systems. Knowing how much surfactant should be used to prepare organo-bentonite is, therefore, critical. The purpose of the present study was to determine the effect of concentration of the cationic surfactant cetyltrimethylammonium bromide (CTAB) adsorbed in organo-bentonite (prepared from two local and commercial raw bentonites with potential for use in adsorbent and composite materials) on the ζ potential, contact angle, and SFE profiles. The raw bentonites were purified using sedimentation and centrifugation techniques prior to preparation of the organo-bentonite. The purification results were evaluated in light of X-ray diffraction (XRD), cation exchange capacity (CEC), free swelling volume (FSV), X-ray fluorescence (XRF), and particle-size analysis data. Most of the gangue minerals (feldspar, calcite, clinoptilolite, opal, quartz, and mica) having particle size >5 μm were removed from the raw bentonites by using a one-stage sedimentation or a Falcon gravity separator (FGS). Higher yields (68.8% and 81.3% for two bentonites) were obtained with the FGS compared to sedimentation while purification levels were almost the same. ζ changed greatly from –35 mV (and –40 mV) toward 38 mV (and 40 mV) with increasing CTAB concentrations. Similar profiles were also obtained for wettability; maximum contact angles for organo-bentonites were measured as ~72–73o, while they were 12.65 and 14.1o for two purified and unmodified bentonites. SFEs were calculated using contact-angle data, and decreased to minimum values of 41.5–43.6 mJ/m2 from 78.6–78.2 mJ/m2 upon treatment of raw bentonites with CTAB. 100–130% CEC concentration was sufficient to prepare organo-bentonites with maximum hydrophobicity and positively charged surfaces.

The reactivity of colloidal particles is regulated by their surface properties. These properties affect the wettability, flocculation-dispersion characteristics, ion exchange, sorption capacities and transport of inorganic colloids. Most studies have focused on hydrophilic, charged-particle surfaces, often ignoring the alterations in surface properties produced by the adsorption of natural organic matter, surfactants and other compounds. Adsorption of these substances can potentially render a surface substantially more hydrophobic. Nevertheless, comparatively little is known about changes in surface properties and reactivity of minerals upon sorption of hydrophobic organic compounds. In this study, the properties of four minerals (kaolinite, pyrophyllite, montmorillonite and Min-U-Sil®) and two inorganic materials (X-ray amorphous Al hydroxide and X-ray amorphous Si oxide) were compared before and after treatment with the common silylating agent, trimethylchlorosilane (TMCS). The samples were characterized by measurements of total carbon, cation exchange capacity (CEC), particle size, specific surface area (SSA), electrophoretic mobility, contact angle, particle aggregation, and by X-ray diffraction and diffuse reflectance infrared spectroscopy. For the layer silicates, surface coverage was limited to ∼2% trimethyl silane (TMSi). TMSi covered 7.5% of the Min-U-Sil® surface and 33% of the X-ray amorphous Si oxide. Treatment did not affect the structure of the minerals but reduced the CEC, SSA and electrophoretic mobilities. Water contact angles increased to between 18 and 114° with treatment. While the apolar characteristic of the surfaces decreased minimally with treatment, the Lewis acid/base properties were substantially reduced and interfacial free energy shifted from positive to negative values indicating a more hydrophobic surface character. For all the samples except kaolinite, these changes affected the stability of the colloids in suspension depending upon solution pH. Although the grafting of TMSi altered colloidal mineral surface properties and increased their hydrophobicity, these changes were not sufficient to predict colloid aggregation behavior.

Greenhouse studies were conducted to investigate the effects of adjuvant and rainfall on bentazon spray retention, efficacy, and foliar washoff in hemp sesbania, sicklepod, smooth pigweed, and velvetleaf. Bentazon was applied at 0.28 to 2.24 kg ai/ha with Agri-Dex, a crop oil concentrate (COC) or Kinetic, an organiosilicone-nonionic surfactant blend (OSB) when weeds were at the three- to five-leaf stage. Plants were subjected to 2.5 cm simulated rainfall for 20 min at 1 and 24 h after application of bentazon. Shoot fresh weight reduction assessed 2 wk after treatment was similar with either adjuvant on velvetleaf and smooth pigweed. OSB enhanced bentazon efficacy in hemp sesbania and sicklepod as compared to COC. Rainfall at 1 h after application generally reduced bentazon activity in all weeds. OSB maintained bentazon activity in hemp sesbania when subjected to rainfall at 1 h after application as compared to COC. Overall, bentazon spray retention on plants was 9 to 550% higher with OSB as compared to COC among the species at 1 h after application. Amount of bentazon residue washed off from the foliage by rainfall within a weed species was relatively similar for both adjuvants except in smooth pigweed and ranged from 39 to 98% among the four weed species at 1 h after application. OSB exhibited specificity for certain weed species and the potential to minimize bentazon spray reaching the soil by increasing deposition.

The effect of oxyethylene (OE) chain length of three homologous series of nonionic surfactants (allinol, nonoxynol, octoxynol) on glyphosate uptake was markedly affected by the leaf surface fine-structure of sugarbeet and kohlrabi. Adaxial leaf surfaces of sugarbeet were covered with a layer of amorphous wax, whereas the adaxial surface of kohlrabi leaves was covered with fine crystalline wax. Foliar uptake of glyphosate (1 mM glyphosate, 20 mM glycine, pH 3.2) averaged 4% for sugarbeet without surfactant, but droplets were not retained by kohlrabi leaves in the absence of a surfactant. Glyphosate absorption with octoxynol (9 to 10 OE units, 0.5 g L−1) was rapid initially (0 to 2 h) and leveled off about 2 h after application in both species. Absorption by sugarbeet decreased from 12 to 3% as OE content of octoxynol was increased from 5 to 30 OE units. In contrast, surfactants of intermediate OE content (octoxynol, 16 OE units) induced the greatest uptake (17%) on kohlrabi. Leaf wetting was markedly affected by surfactant and leaf surface. As OE content of octoxynol increased from 5 to 30 OE units, droplet/leaf interface areas of 1-μl droplets decreased from 4 to 3 mm2 on the adaxial leaf surface of sugarbeet and from 61 to 2 mm2 on kohlrabi. Concurrently, the rate of droplet evaporation (1 μl) decreased from 1.0 to 0.7 nl s−1 on sugarbeet and 4.2 to 0.5 nl s−1 on kohlrabi leaves. The effect of OE content on enhancement of glyphosate uptake and wetting characteristics of spray solutions was similar within species for different hydrophobic moieties but differed markedly between species.

Glyphosate behavior was examined in Italian ryegrass plants from Chile that were sensitive (S) and resistant (R) to this herbicide. In order to explain the resistance to glyphosate, contact angles, spray retention, foliar uptake, herbicide translocation, and target enzyme activity were studied. Contact angles of glyphosate solutions at a field concentration were 40° to 45° on the abaxial surface of R leaves as compared to 70° on S. Glyphosate spray retention by R plants was 35% lower than by S plants. Glyphosate uptake by the abaxial leaf surface of R plants was about 40% lower than that of S plants. In addition, in the R plants more glyphosate migrated to the tip of the treated leaves. The target enzyme in R and S plants was sensitive to the herbicide. Based on these and previous results, it is concluded that resistance in this Italian ryegrass biotype results from lower spray retention, lower foliar uptake from the abaxial leaf surface, and altered translocation pattern. The decreases in spray retention and foliar uptake constitute new mechanisms of glyphosate resistance.

Laboratory and greenhouse studies were conducted on redvine and trumpetcreeper to characterize leaf surface and wax composition, determine responses of these weeds to glyphosate, characterize the nature of interactions between glyphosate and several selective postemergence herbicides (e.g., acifluorfen, bentazon, chlorimuron, imazaquin, and pyrithiobac) used in soybean and cotton, and determine the effects of various adjuvants on glyphosate activity on both species. Trumpetcreeper was consistently more susceptible to glyphosate than redvine. Glyphosate spray solution droplets had lower contact angle in trumpetcreeper than in redvine. Micro-roughness of the trumpetcreeper adaxial leaf surface was greater due to trichomes and glands compared to that of redvine, which had no trichomes or glands. Stomata or crystal wax deposition on the adaxial leaf surface were not observed in either species. The wax mass per unit area (22 to 37 µg cm−2) was similar regardless of the leaf age in both species. Epicuticular wax consisted of hydrocarbons, alcohols, acids, and triterpenes. Wax composition of young leaves of redvine was relatively hydrophilic (72% alcohols and acids, 24% hydrocarbons) compared to the hydrophobic components (23% alcohols and acids, 49% hydrocarbons) of old leaves. In contrast, wax of trumpetcreeper young leaves was relatively hydrophobic (9% alcohols and acids, 29% hydrocarbons), whereas old leaves had similar levels of hydrophilic and hydrophobic components (28% alcohols and acids, 31% hydrocarbons). Glyphosate mixed with selective postemergence herbicides were antagonistic when applied to redvine and trumpetcreeper, except acifluorfen. Various adjuvants did not increase glyphosate efficacy except ammonium sulfate, which increased glyphosate efficacy when applied alone to trumpetcreeper. These results showed that lower glyphosate efficacy was related to the more hydrophobic nature of redvine epicuticular waxes compared to that of trumpetcreeper.

The relationship between surface activity and weed control efficacy of diuron spray solution (0.075 kg ai/ha) with 12 adjuvants (0.1% v/v) was studied in the laboratory and the greenhouse. Organosilicone adjuvants reduced surface tension (ST) and contact angle (CA) of diuron spray solutions to a greater extent than did nonsilicone adjuvants. Three organosilicone adjuvants significantly increased the control and reduced the fresh weight of barnyardgrass. Contact angle was more closely correlated with diuron efficacy than ST, and the coefficient of determination between the CA and the fresh weight or control percent of barnyardgrass was 0.41. Kinetic® applied before or in combination with diuron significantly enhanced diuron efficacy. However, Kinetic sprayed after diuron did not affect the efficacy. Kinetic influenced the retention and absorption of diuron rather than its deposition and translocation.

Sourgrass is a perennial weed infesting annual and perennial crops in Brazil. Three biotypes (R1, R2, and R3) of sourgrass suspected to be glyphosate-resistant (R) and another one (S) from a natural area without glyphosate application, in Brazil, were tested for resistance to glyphosate based on screening, dose-response, and shikimic acid assays. Both screening and dose-response assays confirmed glyphosate resistance in the three sourgrass biotypes. Dose-response assay indicated a resistance factor of 2.3 for biotype R1 and 3.9 for biotypes R2 and R3. The hypothesis of a glyphosate resistance was corroborated on the basis of shikimic acid accumulation, where the S biotype accumulated 3.3, 5.0, and 5.7 times more shikimic acid than biotypes R1, R2, and R3, respectively, 168 h after treatment with 157.50 g ae ha−1 of glyphosate. There were no differences in contact angle of spray droplets on leaves and spray retention, indicating that differential capture of herbicide by leaves was not responsible for resistance in these biotypes. The results confirmed resistance of sourgrass to glyphosate in Brazil.

The level set method is one of the most successful methods for the simulation of multi-phase flows. To keep the level set function close the signed distance function, the level set function is constantly reinitialized by solving a Hamilton-Jacobi type of equation during the simulation. When the fluid interface intersects with a solid wall, a moving contact line forms and the reinitialization of the level set function requires a boundary condition in certain regions on the wall. In this work, we propose to use the dynamic contact angle, which is extended from the contact line, as the boundary condition for the reinitialization of the level set function. The reinitialization equation and the equation for the normal extension of the dynamic contact angle form a coupled system and are solved simultaneously. The extension equation is solved on the wall and it provides the boundary condition for the reinitialization equation; the level set function provides the directions along which the contact angle is extended from the contact line. The coupled system is solved using the 3rd order TVD Runge-Kutta method and the Godunov scheme. The Godunov scheme automatically identifies the regions where the angle condition needs to be imposed. The numerical method is illustrated by examples in three dimensions.

The static shape of drop under electrowetting actuation is well studied and recent electrowetting theory and experiments confirm that the local contact angle (microscopic angle) is unaffected while the apparent contact angle (macroscopic angle) is characterized by the Lippmann-Young equation. On the other hand, the evolution of the drop motion under electrowetting actuation has received less attention. In this paper, we investigate the motion of a conducting water drop on an electrowetting device (EWD) using the level set method. We derive a contact line two-phase flow model under electrowetting actuation using energy dissipation by generalizing an existing contact line model without the electric field. Our model is consistent with the static electrowetting theory as the dynamic contact angle satisfies the static Young's equation under equilibrium conditions. Our steady state results show that the apparent contact angle predicted by our model satisfies the Lippmann-Young's relation. Our numerical results based on the drop maximum deformation agree with experimental observations and static electrowetting theory. Finally, we show that for drop motion our results are not as good due to the difficulty of computing singular electric field accurately. Nonetheless, they provide useful insights and ameaningful first step towards the understanding of the drop dynamics under electrowetting actuation.

The introduction of gases, such as water vapor, into an environmental scanning electron microscope is common practice to assist in the imaging of insulating or biological materials. However, this capability may also be exploited to introduce, or form, liquid phase precursors for electron-beam-induced deposition. In this work, the authors report the deposition of silver (Ag) and copper (Cu) structures using two different cell-less in situ deposition methods—the first involving the in situ hydration of solid precursors and the second involving the insertion of liquid droplets using a capillary style liquid injection system. Critically, the inclusion of surfactants is shown to drastically improve pattern replication without diminishing the purity of the metal deposits. Surfactants are estimated to reduce the droplet contact angle to below ~10°.

This study reports physical and chemical changes that occur at early dentin remineralization stages. Extracted human third molars were sectioned to obtain dentin discs. After polishing the dentin surfaces, three groups were established: (1) untreated dentin (UD), (2) 37% phosphoric acid application for 15 s (partially demineralized dentin—PDD), and (3) 10% phosphoric acid for 12 h at 25° C (totally demineralized dentin—TDD). Five different remineralizing solutions were used: chlorhexidine (CHX), artificial saliva (AS), phosphate solution (PS), ZnCl2, and ZnO. Wettability (contact angle), ζ potential and Raman spectroscopy analysis were determined on dentin surfaces. Demineralization of dentin resulted in a higher contact angle. Wettability decreased after immersion in all solutions. ζ potential analysis showed dissimilar performance ranging from −6.21 mV (TDD + AS) up to 3.02 mV (PDD + PS). Raman analysis showed an increase in mineral components after immersing the dentin specimens, in terms of crystallinity, mineral content, and concentration. This confirmed the optimal incorporation and deposition of mineral on dentin collagen. Organic content reflected scarce changes, except in TDD that appeared partially denatured. Pyridinium, as an expression of cross-linking, appeared in all spectra except in specimens immersed in PS.

We report herein the crystal growth of ZnO nanoparticles by the foam fractionation method. In this study, the vertical column height of the foam was fixed and the velocity of the sparging air was varied, and the effect of foam flow rate on the synthesis of ZnO was investigated. The obtained ZnO consisted of aggregated platelets and had differing ultraviolet absorbances. The as-synthesized ZnO was hydrophobic because of the interaction between the anionic head groups of sodium dodecyl sulfate (SDS) and the ZnO under the precipitation conditions. The long chain of the SDS molecule was the cause of hydrophobicity. The contact angle of water was in the range of 95–105° for the obtained ZnO/SDS surface. The photocatalytic degradation efficiency of the as-synthesized (ZnO/SDS) and the calcined ZnO was investigated for methylene blue, and the calcined ZnO retained its activity even after three recycles.

A small vicinity of a contact line, with well-defined (micro)scales (henceforth the“microstructure”), is studied theoretically for a system of a perfectly wetting liquid,its pure vapor and a superheated flat substrate. At one end, the microstructure terminatesin a non-evaporating microfilm owing to the disjoining-pressure-induced Kelvin effect. Atthe other end, for motionless contact lines, it terminates in a constant film slope(apparent contact angle as seen on a larger scale), the angle being non-vanishing despitethe perfect wetting due to an overall dynamic situation engendered by evaporation. Here wego one step beyond the standard one-sided model by incorporating the effect of vaporpressure non-uniformity as caused by a locally intense evaporation flow, treated in theStokes approximation. Thereby, the film dynamics is primarily affected throughthermodynamics (shift of the local saturation temperature and evaporation rate), thedirect mechanical impact being rather negligible. The resulting integro-differentiallubrication film equation is solved by handling the newly introduced effect (giving riseto the “integro” part) as a perturbation. In the ammonia (at 300   K) example dealt withhere, it proves to be rather weak indeed: the contact angle decreases while the integralevaporation flux increases just by a few percent for a superheat of  ~1   K.However, the numbers grow (roughly linearly) with the superheat.

This paper investigates the flow boiling heat transfer in microchannels with the aim ofdeveloping compact cooling systems which can be adapted to miniaturized power components.Nano- and micro-surface treatments were used as innovative techniques to improve the heattransfer performance as well as to delay the intermittent dryout. It was observed that themicro-structured surfaces show significant enhancements (up to 85%) in heat transfercompared to the smooth surfaces. Especially, using the highly-wetted structured surface,the intermittent dryout is improved.

The electrowetting process is commonly used to handle very small amounts of liquid on a solid surface. This process can be modelled mathematically with the help of the shape optimization theory. However, solving numerically the resulting shape optimization problem is a very complex issue, even for reduced models that occur in simplified geometries. Recently, the second author obtained convincing results in the 2D axisymmetric case. In this paper, we propose and analyze a method that is suitable for the full 3D case.