A Reinterpretation of Organic Liquid-Polytetrafluoroethylene Surface Interactions

The wettability of polytetrafluoroethylene (PTFE) by organic liquids is reanalyzed in terms of dispersion-polar interactions across the liquid-solid interface. The analysis provides values of γ_s ^d = 19.6 dyne/cm, and γ_S ^D = 2.0 dyne/cm for the respective dispersion and polar parts of the surface tension γ_s = 21.6 for PTFE. The definition of a polar contribution to the surface tension of PTFE clarifies detailed aspects of the wettability of this polymer by different homologous liquid series. A modified analytical definition for work of adhesion is developed and applied to this discussion.     

Critical Surface Tension of Acrylamide-Grafted Polypropylene Copolymer by the Contact Angle Method

The contact angles θ of polar liquids on PP-g-AM copolymer (AM content 0.19, 0.26, and 0.37 wt%) were measured. The critical surface tension γ_C of PP-g-AM films were evaluated by the Zisman plot (cos θ versus-γl), the Young-Dupre-Good-Girifalco plot (1 + cos θ) versus 1/γ^0.5 l, and the log(1 + cos θ) versus log-γl plot. The-γl values estimated by the plot log(1 + cos θ) versus log-γl were smaller than those obtained by the other plots.     

Surface energy characterization of modified carbon blacks and its relationship to composites tearing properties

The effects of three types of chemical treatments, i.e. as polar acidic, polar basic, and nonpolar oxidations, on virgin carbon blacks have been studied in terms of pH, acid-base surface values, specific surface area, X-ray diffraction analysis, and surface free energy. The acidic chemical treatment leads to significant changes in surface and adsorption properties, surface free energy, and microstructures. The increased acidic surface functional groups on carbon blacks result from reaction between the basic carbon and the acidic chemical solution. Also, based on the determination of surface free energy from contact angle measurements, a good correlation between the London dispersive component or apolar (γ^d _s) of surface free energy and specific surface area (S_BET) (or crystalline size S along the c-axis, L_C) is shown in this work. Particularly, it is found that the γ^d _s of the carbon blacks studied is highly correlated with the mechanical tearing test results based on hydrocarbon rubber compound composites.     

Studies on the surface free energy and surface structure of PTFE film treated with low temperature plasma

The surface free energy and surface structure of poly(tetrafluoroethylene) (PTFE) film treated with low temperature plasma in O₂, Ar, He, H₂, NH₃, and CH₄ gases are studied. The contact angles of the samples were measured, and the critical surface tension γ_c (Zisman) and γ_c (max) were determined on the basis of the Zisman's plots. Furthermore, the values of nonpolar dispersion force γ^a_s, dipole force γ^b_s, and hydrogen bonding force γ^c_s to the surface tensions for the plasma-treated samples were evaluated by the extended Fowkes equation. Mainly because of the contribution of polar force, the surface free energy and surface wettability of PTFE film which was treated with H₂, He, NH₃, Ar, and CH₄ for a short time increased greatly. Electron spectroscopy for chemical analysis (ESCA) shows that the reason was the decrease of fluorine and the increase of oxygen or nitrogen polar functional group on the surface of PTFE. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1733–1739, 1997     

Contact angle,wetting, and adhesion: a critical review

The theory of the contact angle of pure liquids on solids, and of the determination of the surface free energy of solids, γ_s, is reviewed. The basis for the three components γ^LW _s, γ⊕_s, and γ?_s is developed, and an algebraic expression for these properties in terms of measured contact angles is presented. The inadequacy of the 'two-liquid' methodology (which yields a parameter, 'γ^p') is demonstrated. Attention is given to contact angle hysteresis and to the film pressure, π_e. Some recommendations are made with regard to contact angle measurements. A new treatment of hydrophilicity, and of the scale of hydrophobic/hydrophilic behavior, is proposed. It is shown that there are two kinds of hydrophilic behavior, one due to Lewis basicity (electron-donating or proton-accepting structures) and the other due to Lewis acidity (electron-accepting or proton-donating structures). The properties γ^? and γ^⊕ are the quantitative measures of these types of behavior and they are structurally independent of each other. A triangular diagram, with γ^LW at the hydrophobic corner, and γ^⊕ and γ^? at the two hydrophillic corners, is suggested.     

Surface tension parameters of ice obtained from contact angle data and from positive and negative particle adhesion to advancing freezing fronts

From contact angle data obtained on flat ice surfaces with a number of liquids, combined with data on particle and macromolecule adhesion or non-adhesion to advancing freezing fronts, the apolar (Lifshitz-van der Waals or LW) and polar (Lewis acid-base or AB) surface tension (γ) components and parameters have been determined. At 0°C these are γ^LW _iee = 26.9 and γ^AB _ice = 39.6 mJ/m². The latter consists of an electron-acceptor (γ^⊕) and an electron-donor (γ^?) parameter: γ^⊕ = 14 and γ^? = 28 mJ/m².     

Dispersion-Polar Surface Tension Properties of Organic Solids

A new definition for work of adhesion W_a is applied to computationally define the dispersion γ_s ^d and polar γ_s ^d components of the solid surface tension γ_s = γ_s ^d + γ_s ^d for twenty-five low energy substrates. These calculated surface properties are correlated with surface composition and structure. Surface dipole orientation and electron induction effects are respectively distinguished for chlorinated and partially fluorinated hydrocarbons. Published values for critical surface tension of wetting γ_c are correlated with both γ_s ^d and γ_s.     

Measurement of the Surface Free Energy of Amorphous Cellulose by Alkane Adsorption: A Critical Evaluation of Inverse Gas Chromatography (IGC)

Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ^d _s and γ^d _l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ^d _s was determined to be 71.5 mJ/m², and its temperature dependence was 0.36 mJ m^?2 K^?1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ^d _s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ^d _s and d(γ^d _s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.     

Observations relating to oxygen permeability measurements on membranes

A cell for electrochemically measuring dissolved oxygen permeability coefficients (P_d) has been constructed and tested successfully with Teflon^® FEP membranes of previously established P_d values. Mixtures of n-butyl acrylate, N-vinyl-2-pyrrolidone and a crosslinking agent have been copolymerized to complete conversion via γ-irradiation. Thin discs of the products have been swollen in water to yield new hydrogels with equilibrium water contents (EWC) of 39–73%. The observed exponential increase in P_d with EWC was of a similar form to that reported by other workers for chemically different hydrogels. At a fixed EWC, there was an increase in P_d with thickness of membrane, in accord with the theoretical model for multilayer diffusive transport. However, the results also indicate the effect of the aqueous boundary layer on the measured value of P_d. The need is demonstrated for measurements on highly permeable hydrogels with aqueous environments to be conducted under well-defined transport controlled conditions, if reliable values of P_d are to be obtained.     

Critical Surface Tension of Non-crosslinking Linear Low Density Polyethylene-graft-acrylic Acid by the Contact Angle Method

Abstract

The contact angles θ of polar liquid on surface of non-crosslinking linear low density polyethylene-graft-acrylic acid (LLDPE-g-AA) were measured. The critical surface tension (γ_c) of LLDPE-g-AA films were evaluated by three different plots, the Zisman plot, the Young-Dupre-Good-Girifalco plot, and the log(1 + cos θ) versus log θ _L , plot. The θ _c of LLDPE-g-AA obtained by the 1 + cosθ versus θ _L ^?1/2 plot were higher than those obtained by other plots.     

Study of fretting wear behaviors of FEP

The fretting wear behaviors of perfluorinated ethylene–propylene copolymer (FEP) were studied on an SRV fretting wear tester with the plane contact of FEP against a bearing steel at room temperature of about 15°C. In our tests, the product of load (L) and total sliding distance (S) was preset to be a constant as the wear coefficient K_ω can be expressed as K_ω = W · P_m/(L · S), where W is the volume of material loss, P_m is the flow pressure of the softer material (FEP), L and S are the load and the total sliding distance, respectively. Under our test conditions, no wear of the bearing steel was observed when fretted against FEP. The sudden change of wear rate of FEP or its wear weight was governed by the critical PV value, an important parameter for polymers and polymer composites under sliding friction, which was the product of normal stress and average sliding speed. The critical PV value of FEP under study was 3 × 10⁴ Pa · m/s. It was also found that the topography of wear trace formed on FEP were fairly well corresponding with that of their transferred films on steel surface. Both on worn surface of FEP and on metal surface, three sharply defined regions, wear debris formation region, high-stress region, and slightly sliding wear region, can be distinguished. It indicated that the higher the normal stress, the more difficult the formation of thick transfer film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1119–1125, 1998     

Interfacial Bonding and Environmental Stability of Polymer Matrix Composites

Recently developed adsorption-interdiffusion (A-I) theory of adhesion is employed to isolate the (London) dispersion γ_i,j ^d and (Keesom) polar γ_i,j ^p components of the excess interfacial free energy γ_i,j=γ_i,j ^d+γ_i,j ^p at the fiber-matrix interface in polymer matrix composites. For adsorption bonded interfaces the theory defines a new method of mapping the surface energy effects of an immersion phase upon the Griffith fracture energy γ_G. The stability of interfacial bonding between graphite fiber-epoxy matrix is defined in terms of the theoretical model and experimentally evaluated by accelerated aging studies which monitor changes in fracture energy for crack propagation perpendicular to the fiber axis. Applications of the model to control fiber surface treatments and select matrix components for optimized bond strength and environmental resistance is discussed.     

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.     

Impinging-Jet Ozone Bubble Column Modeling: Hydrodynamics,Gas Hold-up,Bubble Characteristics,and Ozone Mass Transfer

A transient back flow cell model was used to model the hydrodynamic behaviour of an impinging-jet ozone bubble column. A steady-state back flow cell model was developed to analyze the dissolved ozone concentration profiles measured in the bubble column. The column-average overall mass transfer coefficient, k_La (s^?1), was found to be dependent on the superficial gas and liquid velocities, u_G (m.s^?1) and u_L (m.s^?1), respectively, as follows: k_La?=?55.58 · u_G ^1.26· u_L ^0.08 . The specific interfacial area, a (m^?1), was determined as a = 3.61 × 10³ · u_G ^0.902 · u_L ^?0.038 by measuring the gas hold-up (ε _G?=?4.67 · u_G ^1.11 · u_L ^?0.05 ) and Sauter mean diameter, d_S (mm), of the bubbles (d_S?=?7.78 · u_G ^0.207 · u_L ^{? 0.008} ). The local mass transfer coefficient, k_L (m.s^?1), was then determined to be: k_L?=?15.40 · u_G ^0.354 · u_L ^0.118 .     

Enhanced mass transfer using roughened rotating cylinder electrodes in turbulent flow

Cylindrical electrodes have been roughened by machining groove patterns, pyramidal knurling, and superimposing wires and meshes for which the degree of roughness has been calculated. By rotating the electrodes in a turbulent regime, mass transfer for cathodic copper electrodeposition has been measured and the degree of consequent enhancement (relative to an equivalent smooth cylinder) calculated. Typically, the surface area has been increased by 10–40% and the mass transfer rate by 100–300% for turbulent flow defined by 7000<Re<80 000.Nomenclature A (A _R) area of cathodic (rough) cylinder (cm²) - C exponent - C _B metal ion concentration in bulk solution (mol cm^–3) - d _s (d _R) diameter of smooth (rough) cylinders (cm) - D diffusion coefficient of metal ion (cm²s^–1) - F Faraday's constant - I _L limiting current density (mA cm^–2) - j ₀ dimensionless mass transfer factor (=ShSc ^c) - k _L mass transfer coefficient (=I _L/zFC _B) - k _s,k _R k _L values for smooth and rough cylinders - m, n exponents - P pitch, or roughness element spacing (cm) - Re Reynolds number (=Ud/v) - Ré d _R U _R/v - Re _s dU _s/v - Sc Schmidt number (=v/D) - Sh Sherwood number (=k _L d/D) - St Stanton number (=k _L/U) - U _s (U _R) peripheral velocity at smooth (rough) cylinders (cm s^–1) - U ₀ friction velocity (cm s^–1) - w width of wire mesh opening (cm) - z valency change, number of electrons - groove depth (cm) - kinematic viscosity (cm² s^–1) - groove width     

Molecular dissolution behaviors on porous membrane surface using hierarchical metal–organic framework lamellar membrane

Lamellar membranes, especially assembled by microporous framework nanosheets, have excited interest for fast molecular permeation. However, the underlying molecular dissolution behaviors on membrane surface, especially at pore entrances, remain unclear. Here, hierarchical metal–organic framework (MOF) lamellar membranes with 7 nm-thick surface layer and 553 nm-thick support layer are prepared. Hydrophilic (–NH₂) or hydrophobic (–CH₃) groups are decorated at pore entrances on surface layer to manipulate wettability, while –CH₃ groups on support layer provide comparable, low-resistance paths. We demonstrate that molecular dissolution behaviors are determined by molecule–molecule and molecule–pore interactions, derived from intrinsic parameters of molecule and membrane. Importantly, two dissolution model equations are established: for hydrophobic membrane surface, dissolution activation energy (E_S) obeys E_S = K_mln[(γ_L-γ_C)μd²], while turns to E_S=K_aln[(γ_L-γ_C)δ_eμd²] for hydrophilic one. Particularly, hydrophilic pore entrances exert strong interaction with polar molecules, thus compensating the energy consumed by molecule rearrangement, giving fast permeation (>270 L m⁻² h⁻¹ bar⁻¹).     

Contact angles of binary liquids and their interpretation

Contact angles of binary liquid mixtures on Teflon FEP were measured. It was found that the equation of state for interfacial tensions, γ_SL = f (γ_LV, γ_sv), cannot be used to determine solid surface tensions from these contact angles of binary liquid mixtures. These findings are explained in terms of the thermodynamic phase rule.     

IGC study of filler–filler and filler–rubber interactions in silica‐filled compounds

A modification of the existing methods for evaluating the dispersive and specific components of surface free energy (γ_d and γ_s, respectively) was made to investigate filler–rubber and filler–filler interactions by inverse gas chromatography. Four silicas as fillers and various probes that mimic elastomers were employed in this study. It was shown that the pretreatment of silicas with helium could increase γ_d and decrease γ_s. Modification of the silica surface with silane could enhance the dispersive interaction and weaken the specific interaction. The temperature dependence of the interfacial interaction was also investigated, and it was found that lower temperatures favored filler–rubber interactions and mixing efficiency. Tests on different sizes of agglomerates demonstrated the existence of a filler–rubber and filler–filler network. It was also found that γ_d played a role in agglomeration or filler–filler interaction. Our study showed that the larger the specific surface area was, the stronger the dispersive and specific interactions were. The effectiveness of various fillers and elastomer probes was also compared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2517–2530, 2001     

Mass transfer and deodorization efficiency in a countercurrent spray tower for low superficial gas velocities

The aim of this study was to characterize mass transfer and deodorization efficiency in a countercurrent spray tower for low superficial gas velocities. The influence of operating parameters (U_G = 0.005 to 0.025 m s^?1, U_L = 6.1 × 10^?5 to 2.4 × 10^?4 m s^?1) on the liquid retention (ε_L), the drop diameter (d_g), the interfacial area (a) and the overall liquid and gas phase mass transfer coefficients (K_La, K_Ga) were estimated. The spray efficiency of some malodorous compounds was also estimated. A negative influence of the superficial gas velocity was demonstrated, during the spraying of water or chemical neutralizing scrubbing solutions. There was also an increase with the liquid flow rate. Abatements obtained were very good with respect to ammonia (>90%), and acceptable for the other compounds.