Factors influencing contact angle measurements on wood particles by column wicking

The present work focuses on a capillary rise technique, referred to here as column wicking, for determining contact angles on wood particles. The liquid front rise versus time for different probe liquids has been measured for extracted and non-extracted spruce wood particles packed into glass columns. Wood is a porous, heterogeneous, and hygroscopic material. The sorption process of certain polar liquids in the wood substance, i.e. bulk sorption, is exothermic and causes swelling. This bulk sorption process and the resulting release of heat are observed as a distinct temperature increase within the columns during the wicking of water, formamide, and methanol. No temperature increase is observed for ethylene glycol, diiodomethane, and hexane. In some cases, the increase in temperature is observed in advance of the moving visible liquid front line. This may indicate that vapor is moving in advance of the liquid front, resulting in bulk sorption and the corresponding release of heat. An apparent non-linearity is observed when the square of the capillary rise is plotted versus time, mainly for water, formamide, and methanol. This non-linearity is strongly dependent on the probe liquid used and the variation in wood particle size. For the wicking of water, the bulk sorption, and hence the swelling of the wood particles, seems to appear instantaneously at the wetting front line, but for formamide and methanol a time delay is observed. The bulk sorption and resulting swelling of the wood particles strongly influence the determination of the effective interstitial pore radius between the particles, and thus the determination of contact angles by use of the Washburn equation.     

Wicking Technique for Determination of Pore Size in Ceramic Materials

A technique is described for the measurement of mean pore size in ceramics by wicking. Pore size is derived from the measured rates of capillary rise of several apolar, low-energy liquids of known surface tension through thin slices of porous materials, via the Washburn equation. The use of apolar, low-energy liquids assures that the contact angle θ=0° (and cos θ= 1) so that the mean pore radius, R , is the only unknown in the Washburn equation. Fore-size data are presented for two colloidal gel compositions with engineered pore-size distributions. Pore diameters obtained from wicking are found to be smaller than those afforded by merciury porosimetry by a factor of ∼2.     

Organic filler surface analysis by column wicking

Organic fillers derived from biomass waste streams are commonly formulated with phenol-formaldehyde resoles in the production of veneer-based wood composites. The surface characteristics of three fillers, flours of walnut shell (Juglans regia), red alder (Alnus rubra) bark, and corn cob (Zea mays) furfural production residue, were investigated with the column wicking method using the Washburn equation. A series of n-alkanes (spreading liquids) provided reliable estimates of interstitial pore radii, which then enabled contact angle estimates for a variety of non-spreading liquids. Among the three fillers, only alder bark data were complicated by swelling effects, which were eliminated with strict data quality criteria. Corn cob residue exhibited the highest total surface free energy, but all fillers had low energies that were dominated by dispersive effects. The minor polar contributions were basic. Specific surface areas determined from wicking substantially disagreed with Brunauer–Emmett–Teller measurements using N₂ adsorption, where the former were more consistent with measured particle size.     

Darcy's law‐based model for wicking in paper‐like swelling porous media

The wicking of liquid into a paper‐like swelling porous medium made from cellulose and superabsorbent fibers was modeled using Darcy's law. The work is built on a previous study in which the Washburn equation, modified to account for swelling, was used to predict wicking in a composite of cellulose and superabsorbent fibers. In a new wicking model proposed here, Darcy's law for flow in porous media is coupled with the mass conservation equation containing an added sink or source term to account for matrix swelling and liquid absorption. The wicking‐rate predicted by the new model compares well with the previous experimental data, as well as the modified Washburn equation predictions. The effectiveness of various permeability models used with the new wicking model is also investigated. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Low-rate dynamic contact angles on polystyrene and the determination of solid surface tensions

Low-rate dynamic contact angles of 13 liquids on a polystyrene polymer are measured by an automated axisymmetric drop shape analysis – profile (ADSA-P). It is found that 7 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the other 6 liquids, it is found that the liquid-vapor surface tension times cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γ_lvcosθ depends only on γ_lv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and non-inert (polar and non-polar) surfaces (7–13, 24–26). The solid-vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions (33) is found to be 29.8 mJ/m², with a 95% confidence limit of ±0.5 mJ/m² from the experimental contact angles of 6 liquids.     

毛细上升法研究水处理滤料的表面热力学特性

基于Washburn方程用亲油亲水比(LHR)比较了0.9～1.2 mm无烟煤、锰砂和石英砂滤料的润湿性; 同时以正己烷、1-溴萘、甲酰胺和去离子水为探针液, 用Washburn方程和van Oss-Chaudhurry-Good(vCG)理论对滤料表面自由能成分进行了估算。实验测得无烟煤、锰砂和石英砂的LHR值依次为1.93、0.75和0.69, 说明无烟煤的亲油性较好而锰砂和石英砂表现出了亲水性; 估得无烟煤、锰砂和石英砂滤料的表面自由能非极性成分和极性成分依次为38.8、38.0、37.7 mJ·m-2和0.73、6.8、8.7 mJ·m-2,初步说明水处理滤料的表面润湿性与其表面自由能极性成分γABs之间有一定的相关性; 而后者归因于滤料的表面化学组成。     

Studies on surface energetics of glass fabrics in an unsaturated polyester matrix system: Effect of sizing treatment on glass fabrics

The surfaces of glass fibers were sized by polyvinyl alcohol (PVA), polyester, and epoxy resin types in order to improve the mechanical interfacial properties of fibers in the unsaturated polyester matrix. The surface energetics of the glass fibers sized were investigated in terms of contact angle measurements using the wicking method based on the Washburn equation, with deionized water and diiodomethane as the wetting liquids. In addition, the mechanical behaviors of the composites were studied in the context of the interlaminar shear strength (ILSS), critical stress intensity factor (K_IC), and flexural measurements. Different evolutions of the London dispersive and specific (or polar) components of the surface free energy of glass fibers were observed after different sizing treatments. The experimental result of the total surface free energies calculated from the sum of their two components showed the highest value in the epoxy‐sized glass fibers. From the measurements of mechanical properties of composites, it was observed that the sizing treatment on fibers could improve the fiber–matrix interfacial adhesion, resulting in improved final mechanical behaviors, a result of the effect of the enhanced total surface free energy of glass fibers in a composite system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1439–1445, 2001     

Characteristics of Polypeptide/Phospholipid Monolayers on Water and the Plasma-Activated Polyetheretherketone Support

Polyetheretherketone (PEEK) is a highly biocompatible polymer widely used in medicine as an implant production material. In this article, the PEEK surface was characterized in terms of its wettabillity properties after the physicochemical modifications by treatment with the low-temperature air plasma and covering with the Langmuir–Blodgett (LB) monolayers of polypeptide (cyclosporine A, CsA) and/or phospholipid (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC). The LB deposition was preceded by the analysis of miscibility and morphology of monolayers at the air/water interface by means of the Langmuir technique and Brewster angle microscopy (BAM). Then, wettability of the polymer-supported films was evaluated by the contact angle measurements of three probe liquids of different characters (two polar—water and formamide, one apolar—diiodomethane). The measured contact angles allowed for determination of the surface free energy and its components based on the Lifshitz-van der Waals/acid–base (LWAB) approach. Some relations between the kind and magnitude of interactions within the model membranes on the water subphase and those of the PEEK-supported membranes with the liquids were found out. The results allowed obtaining the interesting models of biological coatings with potential applications.     

Determination of the acid-base characteristics of clay mineral surfaces by contact angle measurements-implications for the adsorption of organic solutes from aqueous media

The apolar and the polar (electron-acceptor and electron-donor, or Lewis acid-base) surface tension components and parameters of solid surfaces can be determined by contact angle measurements using at least three different liquids, of which two must be polar. With swelling clay minerals (e.g. smectite clay minerals), smooth contiguous membranes can be fabricated, upon which contact angles can be measured directly. With non-swelling clay minerals (e.g. talc), contact angles can be determined by wicking, i.e. by the measurement of the rate of capillary rise of the liquids in question through thin layers of clay powder adhering to glass plates. The apolar and polar (acid-base) surface tension components and parameters thus found for various untreated and quaternary ammonium base-treated clays allowed the determination of the net interfacial free energy of adhesion of human serum albumin onto the various clay particle surfaces immersed in water. The free energies of adhesion, thus found, correlate well with the experimentally observed degree of adsorption of human serum albumin.     

Darcy's law–based numerical simulation for modeling 3D liquid absorption into porous wicks

Liquid imbibition into polymer wicks, where a clear liquid front can be seen rising during the wicking process, is modeled using the concepts of flow in porous media. The flow of liquid behind the moving liquid front is modeled using the physics of single‐phase flow in a porous medium where the Darcy's law is combined with the continuity equation and a capillary suction pressure is imposed at the liquid front. A novel numerical simulation PORE‐FLOW^© based on the finite element/control volume method is proposed to model such imbibitional flows in wicks of complex shapes. A validation of the simulation is obtained by achieving an excellent comparison of its predictions with an experimental result, an analytical solution, and the Washburn equation for the case of wicking against gravity in a cylindrical wick. The simulation is also used to predict a case of two‐dimensional (2D) wicking in the altered cylindrical wicks with two different cross‐sectional areas. Once again an excellent match is obtained with the experimental results, while analytical solutions for the single and double cross‐section cases along with the Washburn equation fail to predict the 2D wicking. Later, some other types of altered wicks with sharp changes in their cross‐sectional areas were analyzed numerically for their wicking behavior. It was observed that the height of liquid front in a vertical wick as a function of time, which is proportional to the history of liquid imbibed, is strongly dependent on the extent of reduction in the wick cross‐sectional area as well as its location vis‐à‐vis the wick entrance. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Low-rate Dynamic Contact Angles on Poly(methyl methacrylate/n-butyl methacrylate) and the Determination of Solid Surface Tensions

Low-rate dynamic contact angles of 12 liquids on a poly(methyl methacrylate/n-butyl methacrylate) P(MMA/nBMA) copolymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 6 liquids yield non-constant contact angles, and/or dissolve the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid- vapour surface tension times the cosine of the contact angle changes smoothly with the liquid-vapour surface tension, i.e., γ_iv cos θ depends only on γ_iv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and noninert (polar and non-polar) surfaces [34-42, 51 -53]. The solid-vapour surface tension calculated from the equation-of-state approach for solid -liquid interfacial tensions [14] is found to be 34.4 mJ/m², with a 95% confidence limit of \pm 0.8mJ/m², from the experimental contact angles of the 6 liquids.     

On the use of Washburn's equation for contact angle determination

A systematic study on the possibility of Young's contact angle determination from Washburn's equation was performed using the so-called thin-layer wicking technique in which the rate of penetration of a liquid into the porous layer of a solid is measured. Commercial (Merck) SiO₂ deposited on the glass plate for thin-layer chromatography was used as a model solid and n-alkanes (from pentane to hexadecane), diiodomethane, and α-bromonaphthalene were employed as the probe liquids. It was shown that the contact angle calculated from Washburn's equation was not equal to Young's contact angle of a drop of the same liquid, placed on a flat surface of the solid. Consequently, the solid surface free energy components calculated using contact angles from Washburn's equation are not the true values. However, the approach previously suggested by us has been verified again, as it gives consistent values of the surface free energy components determined from all the liquids used.     

Effect of fatigue loading on wicking properties of polyamide 66 nanofiber yarns

The wicking phenomenon is of prime importance with regards to biomedical applications of nanofiber yarns such as suture yarns and tissue scaffolds. In such applications, the yarns are usually subjected to cyclic tensile forces and biological tensile stresses. There is a lack of science behind the effect of fatigue on wicking properties of nanofiber yarns and this work aims at exploring this venue. Wicking properties of polyamide 66 nanofiber yarns are investigated by tracing the color change in the yarn structure resulting from pH changes during the capillary rise of distilled water. Results show that applying cyclic loading increases equilibrium wicking height in the Lucus–Washburn equation, which is attributed to changes in the overall pore structure in the cyclic loaded yarn. The likely causes of these changes are studied by scanning electron microscope, which reveals disentangled, more or less aligned and parallel nanofibers with a smaller radius in the nanofibrous structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47206.     

Surface properties of EPDM,silicone rubber,and their blend during aging

Surface energy of EPDM, silicone rubber, and their 50 : 50 (by weight) blend during aging was determined by contact angle measurement using water and formamide as the probe liquids. The surface energy increases initially with aging time. The results are explained on the basis of the polar component of the surface energy. Blending offers a good degree of protection toward aging of EPDM rubber. The generation of polar groups during aging is confirmed by IR and ESCA investigations. © 1995 John Wiley & Sons, Inc.     

有机液体在粉末上接触角的测定研究

得到了一系列有机液体在粉末上的接触角的数值和表面活性剂在这些粉末上表现的性质,并做了定性和定量分析。实验原理建立在把渗透的液体进入玻璃管内粉末形成的多孔塞基础上,将Washburn方程用于毛细管内液体的流动用于计算液体和粉末之间接触角大小。结果显示了有机液体分子在石墨、铝粉上表面吸附的细节,并讨论其在科研和生产实践中的应用。     

Impact of Organic Solvents on Physicochemical Properties of Nanofiltration and Reverse‐Osmosis Membranes

Polymeric membranes subjected to the permeation of n‐hexane were characterized and the influence of pretreatment with ethanol on the properties of the membranes was studied to assess membrane performance and stability. The results suggest that the selectivity of the membrane depends not only on the pore size, but also to a great extent on the interaction between solvent and polymer. An increase in membrane roughness and contact angle was observed for all membranes after pretreatment with ethanol and n‐hexane permeation. Moreover, the surface free energy decreased after solvents exposure, indicating an increase in membrane surface hydrophobicity and polymer swelling. The studied membranes show feasibility of use for the recovery of solvents, if suitable process parameters are selected.     

Time‐dependent changes of surface properties of polyether ether ketone caused by air plasma treatment

The effect of air plasma treatment on wetting and energy properties, surface composition and morphology of polyether ether ketone (PEEK) was investigated. The influence of the storage time on the surface properties of plasma‐treated polymer plate was also examined. The properties were determined by advancing and receding contact angle measurements, Fourier transform infrared spectroscopy supported by theoretical spectrum modelling, X‐ray photoelectron spectroscopy and optical profilometry. Three theoretical approaches were used in the determination of the apparent surface free energy of the untreated and plasma‐treated PEEK samples from the measured contact angles of probe liquids (water, formamide, diiodomethane): the contact angle hysteresis method, the Owens and Wendt approach and the Lifsthitz ? van der Waals acid–base approach. It was found that air plasma treatment of PEEK causes significant chemical and morphological changes of the polymer surface, which are reflected in the decrease of contact angles from 83.4° to 11.7° for water after 180 s plasma treatment. This is due to the formation of polar functional groups resulting in the increase of the surface hydrophilicity. After plasma treatment the apolar component of the surface free energy practically does not change, while the polar component increases significantly, especially for plates treated for 180 s, from 0 to 19.6 mJ m^?2. In addition, the modified PEEK surface is not stable during storage and it acquires more hydrophobic character. © 2016 Society of Chemical Industry     

Chain Conformation and Surface Characteristics of Polymers

Films of styrene-butyl acrylate copolymers when pre-conditioned in polar or non-polar media, have been used for measurements of critical surface tension, for retention volume measurements by inverse gas chromatography, and as adhesives in joints with aluminium sheet. It has been shown that large variations in surface tension, and particularly in the non-dispersive force contribution, are generated by exposing the polymer to diverse media. Specific retention volumes indicate that the copolymer surface becomes enriched in polar groups when exposed to polar media including water and formamide. The peel strength of Al-polymer joints can be roughly doubled when the polymer surface is pre-conditioned in polar rather than in non-polar media. The magnitude of property variations diminishes with increasing content of the acrylic moiety in the polymer.

The results are interpreted as showing that the surface conformation of polymer chains is such as to diminish or enrich the surface concentration of polar moieties, depending on whether the polymer is in contact with polar or non-polar media. The proposed surface re-conformation appears to be reversible, and to proceed by diffusion-dependent rate processes. This evidence elaborates on the importance of attenuated responses in macromolecules to physico-chemical forces, and on the consequences of these responses to bulk as well as surface and interfacial properties of the polymer.     

A study of the applicability of the capillary rise of aqueous solutions in the measurement of contact angles in powder systems

The rate of wetting of a powder bed was studied in terms of the wetting parameters, liquid surface tension and powder/liquid contact angle, using three carbon black powders and aqueous solutions of surfactants and organic liquids. The rate of capillary rise of pure organic liquids through a powder bed can be described by the Washburn equation, and when compared with the behavior of aqueous surfactant solutions, it showed that deviations from linearity of the latter are attributable to adsorption of surfactant on the solid surface with resultant depletion of solute from the liquid phase. Agreement between Washburn capillary rise results and sessile drop results was observed whenever adsorption was absent.