The surface energy of kaolinite

The surface energy of kaolinite was determined from the water adsorption isotherm, the water/kaolinite contact angle, and the surface tension of water, using a formula obtained by combining the Young equation with the general equation of pair interaction. This formula could be represented by a polynomial function whose roots gave one real value of 252.57±2.75 mJ m^–2 for the surface energy of kaolinite. An important feature of the procedure for obtaining this energy is the use of the Young equation to determine the range in which the value of the surface energy lies.     

Forces between polyethylene surfaces in oxyethylene dodecyl ether solutions as influenced by the number of oxyethylene groups

The atomic force microscopy (AFM) colloidal probe technique was used to study the effect of oxyethylene dodecyl ethers, C12En (n = 1-7), on interactions between hydrophobic polyethylene (PE) surfaces in aqueous solutions. Long-range (colloidal) and contact (pull-off) forces were measured between 10 to 20 microm PE spheres and a flat PE surface at concentrations of surfactant of 1 x 10(-6) and 1 x 10(-4) M. The surface tension of the surfactant solutions and contact angles at PE surfaces were also studied. The influence of the number of oxyethylene groups in the surfactant molecule was examined. Initially, long-range attractive (hydrophobic) forces between the PE surfaces were observed that decreased in range and magnitude with an increase in the number of oxyethylene groups in 1 x 10(-4) M solutions. Above four oxyethylene groups per molecule, repulsive forces were observed. The measured pull-off force between PE surfaces decreased monotonically from approximately 500 mJ/m2 for C12E1 to 150 mJ/m2 for C12E7. The interfacial energy was calculated on the basis of the JKR model, taking into account long-range forces operating outside the contact area. The interfacial energies decreased from 43-47 mJ/m2 for PE-water and PE-C12E1 (1 x 10(-4) M) interfaces to approximately 18 mJ/m2 for PE-C12E7 (1 x 10(-4) M). The interfacial energy was also calculated from measured contact angles and surface tensions using Neumann's equation of state and Young's equation. A similar relationship between interfacial energy and the number of oxyethylene groups was observed on the basis of contact and surface tension measurements. However, interfacial energy values were smaller, within 15-20 mJ/m2, than those calculated from AFM pull-off force measurements.     

Effect of concentration of trimethylchlorosilane (TMCS) and hexamethyldisilazane (HMDZ) silylating agents on surface free energy of silica aerogels

The surface free energy of a solid determines its surface and interfacial behavior in processes like wetting and adhesion which is crucial for silica aerogels in case of organic liquid absorption and transportation of chemicals at nano-scale for biotechnological applications. Here, we have demonstrated that the surface free energy of aerogels can be tuned in wide range from 5.5892 to 0.3073 mJ/m(2) by modifying their surface using TMCS and HMDZ silylating reagents. The alcogels were prepared by two step acid-base catalyzed process where the molar ratio of precursors Tetraethoxysilane (TEOS):Methanol (MeOH):Oxalic acid:NH(4)OH:NH(4)F was kept at optimal value of 1:2.7:0.18×10(-4):0.02:0.22×10(-3), respectively. To modify gel surfaces, TMCS and HMDZ concentration have been varied from 3% to 12% and such alcogels were dried at ambient pressure. It is observed from FTIR for aerogels that increase in concentration of silylating reagent resulted increase in hydrophobicity. This leads to increase in contact angle for water from 123° to 155° but leads to decrease in surface free energy from 5.5892 to 0.3073 mJ/m(2). As there is not direct method, we have used Neumann's equation of state to estimate surface energy of aerogels.     

On Neglecting the Polar Nature of Halogenated Hydrocarbons in the Surface Energy Determination of Polar Solids from Contact Angle Measurements

The generally accepted strategy of neglecting the polar nature of halogenated liquids in the surface energy determination using the Lifshitz-van der Waals/Lewis acid-base (LW/AB) approach may lead to erroneous and inconsistent results for polar solids. This was demonstrated in a simulation study carried out on monopolar basic surfaces using water, glycerol, and hypothetical liquids whose surface energy characteristics (gamma(L)(LW)=50 mJ/m(2), gamma(L)(-)=0, and gamma(L)(+)=0-1 mJ/m(2)) were chosen to approximate halogenated hydrocarbons. Neglect of the liquid polarity overestimates the LW component and underestimates the basic parameter of the solid surface energy. This effect increases rapidly with an increase in the actual (nonzero) gamma(L)(+) value of supposedly apolar liquid. Consequently, results with an appropriate level of precision can be obtained only with liquids having gamma(L)(+)<0.02 mJ/m(2). For liquids having gamma(L)(+) approximately 0.5 mJ/m(2) (diiodomethane, s-tetrabromoethane, and, probably, other halogenated hydrocarbons), neglect of the liquid polarity causes errors up to 15% in the LW component and up to 100% in the basic parameter of the solid surface energy. The quantitative trends established in the simulation study were indeed observed in an experimental study performed on the surfaces of poly(methyl methacrylate) and polystyrene using water, glycerol, and diiodomethane or s-tetrabromoethane as the test liquids. Copyright 2000 Academic Press.     

Surface free energy of sulfur--revisited I. Yellow and orange samples solidified against glass surface

Surface free energy of two different samples of solidified sulfur (yellow and orange) was investigated, using several approaches for its determination. It was found that values determined about two decades ago for surface free energy of sulfur were overestimated. From current studies the apparent value of this energy ranges between 30 and 60 mJ/m(2), depending on the kind and age of the sulfur samples (up to 1 year old) and/or the probe liquid used for the advancing and receding contact angle measurements. The energy has been calculated from van Oss et al.'s approach (Lifshitz-van der Walls, electron-donor, and electron-acceptor components), the contact angle hysteresis approach proposed by Chibowski, the equation of Owens and Wendt (dispersion and polar components), and Neumann et al.'s equation of state, as well as from equilibrium contact angle using Tadmor's procedure. The lowest values of the energy for 3-day- and 3-month-old samples of sulfur were calculated from the equation of state; they were below the range mentioned above.     

Thermoresponsive poly(N-isopropylacrylamide) copolymers: contact angles and surface energies of polymer films

Surface properties of poly(N-isopropylacrylamide) (PNIPAM) copolymer films were studied by contact angle measurements and optical and atomic force microscopy. We prepared a series of copolymers of N-isopropylacrylamide with N-tert-butylacrylamide (NtBA) in order of increasing hydrophobicity. The measurements of the advancing contact angle of water at 37 degrees C were hampered by the observation of a distinct stick/slip pattern on all polymers in the series with the exception of poly(NtBA) (PNtBA). We attributed this behavior to the film deformation by the vertical component of liquid surface tension leading to the pinning of the moving contact line. This was confirmed by the observation of a ridge formed at the pinned contact line by optical microscopy. However, meaningful contact (without the stick/slip pattern and with a time-independent advancing contact angle) angles for this thermoresponsive polymer series could be obtained with carefully selected organic liquids. We used the Li and Neumann equation of state to calculate the surface energy and contact angles of water for all polymers in the series of copolymers and van Oss, Chaudhury, and Good (vOCG) acid-base theory for PNtBA. The surface energies of the thermoresponsive polymers were in the range of 38.9 mJ/m2 (PNIPAM) to 31 mJ/m2 (PNtBA) from the equation of state approach. The surface energy of PNtBA calculated using vOCG theory was 29.0 mJ/m2. The calculated contact angle for PNIPAM (74.5 +/- 0.2 degrees ) is compared with previously reported contact angles obtained for PNIPAM-modified surfaces.     

Surface and thermodynamic characterization of conducting polymers by inverse gas chromatography. I. Polyaniline

The surface thermodynamic characteristics of both doped polyaniline (PANI-HEBSA) and the non-conducting form (PANI-EB) were investigated using inverse gas chromatography. Fourteen solutes were injected into two separate chromatographic columns containing PANI-EB and PANI-HEBSA. All solutes interacted strongly with the conducting form PANI-HEBSA; in particular, undecane and dodecane showed stronger interaction due to the increase of the dispersive forces. Methanol and ethanol showed stronger H-bonding with the conducting form than propanol and butanol. A curvature was observed for acetates and alcohols with a maximum of around 145 degrees C as an indication of a phase change from a semicrystalline to amorphous phase. DeltaH(l)s value increased considerably (-3.35 to -46.44 kJ/mol) while the deltaH(l)s for the undoped PANI (PANI-EB) averaged about -0.03 kJ/mol. PANI-EB-alkane interaction parameters were measured and ranged from +0.40 to +1.50 (endothermic). However, PANI-HEBSA showed an exothermic behavior due to the polar surface (-1.50 to +1.2). Interaction parameters decreased as the temperature increased and are characteristic of the strong interaction. The dispersive surface energy of the non conducting PANI-EB ranged from 29.13 mJ/m2 at 140 degrees C to 94.05 mJ/m2 at 170 degrees C, while the surface energy of the conducting PANI-HEBSA showed higher values (150.24 mJ/m2 at 80 degrees C to 74.27 mJ/m2 at 130 degrees C). Gamma(s)d values for PANI-EB were found to be higher than expected. The trend of the gamma(s)d change direction is also surprising and unexpected due to the thermal activation of the surface of the polymer and perhaps created some nano-pores resulting in an increase in surface energy of the non-conducting form.     

The adsorption of cetyltrimethylammonium bromide and propanol mixtures with regard to wettability of polytetrafluoroethylene II. Adsorption at polytetrafluoroethylene-aqueous solution interface and wettability

Measurements of contact angles (theta) of aqueous solutions of cetyltrimethylammonium bromide (CTAB) and propanol mixtures at constant CTAB concentration equal to 1x10(-5), 1x10(-4), 6x10(-4) and 1x10(-3) M on polytetrafluoroethylene (PTFE) were carried out. The obtained results indicate that the wettability of PTFE by aqueous solutions of these mixtures depends on their composition and concentration. They also indicate that, contrary to Zisman, there is no linear relationship between cos theta and the surface tension (gamma(LV)), but a linear relationship exists between the adhesional (gamma(LV)cos theta) and surface tension of aqueous solutions of CTAB and propanol mixtures. Curve gamma(LV)cos theta vs gamma(LV) has a slope equal -1 suggesting that adsorption of CTAB and propanol mixtures and the orientation of their molecules at aqueous solution-air and PTFE-aqueous solution interfaces is the same. Extrapolating this curve to the value of gamma(LV)cos theta corresponding to theta=0, the value of the critical tension of PTFE wetting equal 23.4 mN/m was determined. This value was higher than that obtained from contact angles of n-alkanes on PTFE surface (20.24 mN/m). The difference between the critical surface tension values of wetting probably resulted from the fact that at cos theta=1 the PTFE-aqueous solution of CTAB and propanol mixture interface tension was not equal to zero. This tension was determined on the basis of the measured contact angles and Young equation. It appeared that the values of PTFE-aqueous solution of the CTAB and propanol mixtures interface tension can be satisfactorily determined by modified Szyszkowski equation only for solutions in which probably CTAB and propanol molecules are present in monomeric form. However, it appeared that using the equation of Miller et al., in which the possibility of aggregation of propanol molecules in the interface layer is taken into account, it is possible to describe the PTFE-solution interfacial tension for all systems studied in the same way as by the Young equation. On the basis of linear dependence between the adhesional and surface tension it was established that the work of adhesion of aqueous solution of CTAB and propanol mixtures does not depend on its composition and concentration, and the average value of this work was equal to 46.85 mJ/m(2), which was similar to that obtained for adhesion of aqueous solutions of two cationic surfactants mixtures to PTFE surface.     

The surface energy of montmorillonite

By combining the relation that describes pair interaction in binary mixtures with the Young equation, a formula is obtained for calculating the surface energy of montmorillonite as a function of the surface pressure, the surface tension of water, and the liquid/solid contact angle. The formula is an equation of an inverted parabola, which could be represented by a polynomial function. Roots of the polynomial gave one real value of 205.066+/-2.764 mJm(-2) for the surface energy of montmorillonite. The value obtained is of the expected magnitude and probably is better than those obtained by previous approaches.     

固体表面能色散成分的测定

Tamai, Hamilton, Carre等曾通过测量烷烃-水双液参照体系在固体表面的接触角,采用基于界面非色散成份的均方关系, 计算了高表面能固体的表面能色散成份(γs^d)及非色散成份(γs^p), 对此计算方法, Fowkes曾给予批评, 提出界面能的非色散成份主要来源于酸碱配位作用, 基于非色散成份均方关系的计算不能正确反映实际情况, 本研究改进了由双液法接触角值计算γs^d值的方法。     

Molding block copolymer micelles: a framework for molding of discrete objects on surfaces

Soft lithography based on photocurable perfluoropolyether (PFPE) was used to mold and replicate poly(styrene-b-isoprene) block-copolymer micelles within a broad range of shapes and sizes including spheres, cylinders, and torroids. These physically assembled nanoparticles were first formed in a selective solvent for one block then deposited onto substrates having various surface energies in an effort to minimize the deformation of the micelles due to attractive surface forces. The successful molding of these delicate nanoparticles underscores two advantages of PFPE as a molding material. First, it allows one to minimize particle deformation due to adsorption by using low energy substrates. Second, PFPE is not miscible with the organic micelles and thus prevents their dissociation. For spherical PS-b-PI micelles, a threshold value of the substrate surface energy for the mold to lift-off cleanly, that is, the particles remain adhered to the substrate after mold removal was determined to be around gamma congruent with 54 mJ/m2. For substrates with higher surface energies (>54 mJ/m2), the micelles undergo flattening which increase the contact area and thus facilitate molding, although at the expense of particle deformation. The results are consistent with theoretical predictions of a molding range for substrate surface energies, which depends on the size, shape, and mechanical properties of the particles. In a similar fashion, cylindrical PS-b-PI micelles remain on the substrate at surface energies gamma>or=54 mJ/m2 after a mold removal. However, cylindrical micelles behaved differently at lower surface energies. These micelles ruptured due to their inability to slide on the surfaces during mold lift-off. Thus, the successful molding of extended objects is attainable only when the particle is adsorbed on higher energy substrates where deformation can still be kept at a minimum by using stronger materials such as carbon nanotubes for the master.     

Solid surface mapping by inverse gas chromatography

Inverse gas chromatography (IGC) at infinite dilution, is a technique for characterising solid surfaces. Current practice is the injection of n-alkane homologous series to obtain the free energy of adsorption of the CH2 group, from which the London component of the solid surface free energy, gamma(d)s, is calculated. A value around 40 mJ/m2 is obtained for poly(ethylene), and 30 mJ/m2 for a clean glass fibre, while the potential surface interactivity of a glass fibre is far greater than that of poly(ethylene). A specific component of the surface, in mJ/m2, should be calculated in order to obtain significant parameters. As applied up to date, when calculating the specific component of the surface energy, the fact that W(sp)a energy values are in a totally different scale than AN or DN values is a major drawback. Consequently, Ka and Kb values obtained are in arbitrary energy units, different from those of the London component measured by injecting the n-alkane series. This paper proposes a method to obtain Ka and Kb values of the surface in the same energetic scale than the London component. The method enables us to correct the traditional London component of a solid, obtaining a new value, where the amount of WaCH2 accounting for Debye interactions with polar sites, is excluded. As a result, an approach to surface mapping is performed in several different substrate materials. We show results obtained on different solid surfaces: poly(ethylene), clean glass fibre, glass beads, chemically modified glass beads and carbon fibre.     

Surface properties and structures of diblock copolymer and homopolymer with perfluoroalkyl side chains

The surface free energy of diblock copolymer, composed of methyl methacrylate and 2-perfluorooctylethyl methacrylate (PMMA-b-PFEMA), was compared with that of PFEMA homopolymer (P-PFEMA) in correlation with their structures in the solid state and in the solution using dynamic contact angle, X-ray photoelectron spectroscopy, X-ray diffraction, and dynamic light scattering. The PMMA-b-PFEMA film cast from chloroform solution was found to possess very low surface free energy (7.8 mJ/m(2)) compared with the surface free energies of the P-PFEMA (8.5 mJ/m(2)) and the PMMA-b-PFEMA (9.8 mJ/m(2)) films cast from CF(3)CF(2)CHCl(2) solutions. These differences in the surface free energy were brought about by the variations in their surface structures. The very low surface free energy was considered to have originated from the surface segregation of the PFEMA segments highly self-assembled by the presence of chloroform.     

Changes in wetting properties of alumina surface treated with DPPC in the presence of phospholipase A2 enzyme

Wetting properties of commercial Al(2)O(3) plates contacted with dipalmitoylphosphatidylcholine (DPPC) or DPPC+enzyme (phospholipase PLA(2)) in NaCl solution were determined by thin layer wicking and with the help of Washburn equation. Van Oss et al.'s approach to interfacial free energy interactions was applied to determining the solid surface free energy components. Wicking experiments were performed both for bare and alumina plates precontacted overnight with the probe liquid saturated vapours, as well as the untreated and DPPC (or DPPC+PLA(2)) treated alumina plates. For this purpose the penetration rates of n-octane, water and formamide were measured. From these experiments it resulted that original alumina surface is strongly polar with electron-donor interactions originating from the surface hydroxyl groups. Adsorption of DPPC on Al(2)O(3) plates slightly increased the hydrophobic character of the alumina surface (considerable decrease of the electron-donor, γ(s)(-) parameter and γ(s)(AB) component was visible) in such a way that the hydrocarbon chains were directed outwards and the polar part towards the alumina surface. However, after the enzyme action the products of DPPC hydrolysis by PLA(2) (palmitic acid and lysophosphatidylcholine) increased again the hydrophilic character of Al(2)O(3) surface (a minor increase in γ(s)(AB) component and drastic increase of the electron-donor γ(s)(-) parameter was noticeable). After treatment with DPPC or DPPC+enzyme PLA(2) solution the changes of the total surface free energy of alumina and its Lifshits-van der Waals (γ(s)(LW)) component were in the range 7-10 mJ/m(2), but the most considerable and delivering more interesting information were the changes of the electron-donor (γ(s)(-)) parameter ranging from 27 to 35 mJ/m(2). Moreover, the changes of the alumina surface wettability were dependent on the time of the enzyme contacting with DPPC in NaCl solution. On the basis of the obtained results it seems that the thin layer wicking method can be an additional useful tool in investigations of the effect of phospholipid and PLA(2) action on the hydrophilic-hydrophobic character of alumina surface.     

Determination of chromium in the surface nano-layer covering the Zn-based anti corrosion coating of steel sheets using a laser-induced breakdown spectrometry

A method was proposed for the determination of Cr in a thin surface nanolayer deposited on top of a micrometrical Zn-based anticorrosive coating of steel sheets using laser-induced breakdown spectrometry (LIBS). Optimization of the LIBS parameters was performed with respect to the statistical parameters of regression, these being the coefficient of determination (R ²), akaike information criterion and mean-squared prediction error. These were calculated for curves describing the relationship between the Cr surface concentration and the intensity of LIBS signal. The most critical parameter of analysis appears to be the focal spot diameter. When its value was 200 μm and corresponding energy density (fluence) had value of 413.8 J/cm², the intensity–concentration relationship revealed a negative slope. This phenomenon was caused by the difference in total ablated volume for samples with a different content of Cr in the surface layer. This phenomenon was not observed for higher values of the focal spot diameter (400 and 500 μm) and lower values of fluence (103.5 and 66.2 J/cm²). A range of calibration obtained under optimal conditions (focal spot diameter of 400 μm; single pulse mode, laser pulse energy of 130 mJ) was 11–21 mg/m² and the limit of detection was 0.7 mg/m². The recovery values calculated from the results of the proposed LIBS method and the standard ED XRF method ranged from 99.2 to 101%.     

有机膦与聚合物抑制剂对氟硅酸钠（钾）结垢性能的协同抑制作用

采用浊度法和静态抑垢法,研究了抑制剂2-膦酸基-1,2,4-三羧酸丁烷(PBTCA)与水解聚马来酸酐（HPMA）对氟硅酸钠（钾）结晶的影响。 运用经典结晶成核理论解释了抑制机理,利用扫描电子显微镜和X射线衍射技术表征了氟硅酸钠（钾）的晶体形貌和晶型。 结果表明,PBTCA与HPMA通过提高氟硅酸钠（钾）结晶时的表面自由能而抑制氟硅酸钠（钾）的析出。 PBTCA与HPMA之间存在明显的协同作用,PBTCA与HPMA共同作用使Na2SiF6的结晶表面自由能从108 mJ/m2升高至126 mJ/m2,溶液中Na+的阻垢率从6.2%上升至70.3%;使K2SiF6的结晶表面自由能从199 mJ/m2升高至230 mJ/m2,溶液中K+的阻垢率从10.2%升高至45.3%。 PBTCA与HPMA的加入使氟硅酸钠（钾）的粒径变小,颗粒分散;空白溶液中晶体主要为NaKSiF6,PBTCA与HPMA混合体系中结晶产物主要为Na2SiF6和K2SiF6。     

Effect of compressed bovine lipid extract surfactant films on oxygen transfer

In the lungs, oxygen transfer from the inspired air to the capillary blood needs to cross the surfactant lining layer of the alveoli. Therefore, the gas transfer characteristics of lung surfactant film are of fundamental physiological interest. However, previous in vitro studies-most relied on the Langmuir-type balance-fail to cover the low surface tension range (i.e., less than the equilibrium surface tension of approximately 25 mJ/m2) due to film leakage. We have recently developed a novel in vitro experimental strategy, the combination of axisymmetric drop shape analysis and captive bubble technique (ADSA-CB), in studying the effect of surfactant films on interfacial gas transfer (Langmuir 2005, 21, 5446). In the present work, ADSA-CB is used as a micro-film-balance to study the effect of compressed bovine lipid extract surfactant (BLES) films on oxygen transfer. A low surface tension ranging from approximately 25 mJ/m2 to 2 mJ/m2 is studied. The experimental results suggest that lung surfactant films at a low surface tension near 2 mJ/m2 provide resistance to oxygen transfer, as indicated by a decrease of 30-50% in the mass transfer coefficient (kL) of oxygen in BLES suspensions with respect to water. At higher surface tension (i.e., >6 mJ/m2), the resistance to oxygen transfer is only modest, i.e., the decrease in kL is less than 20% compared to water. The experimental results suggest that lung surfactant plays a role in oxygen transfer in the pulmonary system.     

Interaction energy and surface reconstruction between sheets of layered silicates

Interactions between two layered silicate sheets, as found in various nanoscale materials, are investigated as a function of sheet separation using molecular dynamics simulation. The model systems are periodic in the xy plane, open in the z direction, and subjected to stepwise separation of the two silicate sheets starting at equilibrium. Computed cleavage energies are 383 mJ /m(2) for K-mica, 133 mJ /m(2) for K-montmorillonite (cation exchange capacity=91), 45 mJ /m(2) for octadecylammonium (C(18))-mica, and 40 mJ /m(2) for C(18)-montmorillonite. These values are in quantitative agreement with experimental data and aid in the molecular-level interpretation. When alkali ions are present at the interface between the silicate sheets, partitioning of the cations between the surfaces is observed at 0.25 nm separation (mica) and 0.30 nm separation (montmorillonite). Originally strong electrostatic attraction between the two silicate sheets is then reduced to 5% (mica) and 15% (montmorillonite). Weaker van der Waals interactions decay within 1.0 nm separation. The total interaction energy between sheets of alkali clay is less than 1 mJ /m(2) after 1.5 nm separation. When C(18) surfactants are present on the surfaces, the organic layer (>0.8 nm) acts as a spacer between the silicate sheets so that positively charged ammonium head groups remain essentially in the same position on the surfaces of the two sheets at any separation. As a result, electrostatic interactions are efficiently shielded and dispersive interactions account for the interfacial energy. The flexibility of the hydrocarbon chains leads to stretching, disorder, and occasional rearrangements of ammonium head groups to neighbor cavities on the silicate surface at medium separation (1.0-2.0 nm). The total interaction energy amounts to less than 1 mJ /m(2) after 3 nm separation.     

Low temperature properties of acetonitrile confined in MCM-41

The effect of confinement on the phase changes and dynamics of acetonitrile in mesoporous MCM-41 was studied by use of adsorption, FT-IR, DSC, and quasi-elastic neutron scattering (QENS) measurements. Acetonitrile molecules in a monolayer interact strongly with surface hydroxyls to be registered and perturb the triple bond in the C[triple bond]N group. Adsorbed molecules above the monolayer through to the central part of the cylindrical pores are capillary condensed molecules (cc-acetonitrile), but they do not show the hysteresis loop in adsorption-desorption isotherms, i.e., second order capillary condensation. FT-IR measurements indicated that the condensed phase is very similar to the bulk liquid. The cc-acetonitrile freezes at temperatures that depend on the pore size of the MCM-41 down to 29.1 A (C14), below which it is not frozen. In addition, phase changes between alpha-type and beta-type acetonitriles were observed below the melting points. Application of the Gibbs-Thomson equation, assuming the unfrozen layer thickness to be 0.7 nm, gave the interface free energy differences between the interfaces, i.e., Deltagamma(l/alpha) = 22.4 mJ m(-2) for the liquid/pore surface (ps) and alpha-type/ps, and Deltagamma(alpha/beta) = 3.17 mJ m(-2) for alpha-type/ps and beta-type/ps, respectively. QENS experiments substantiate the differing behaviors of monolayer acetonitrile and cc-acetonitrile. The monolayer acetonitrile molecules are anchored so as not to translate. The two Lorentzian analysis of QENS spectra for cc-acetonitriles showed translational motion but markedly slowed. However, the activation energy for cc-acetonitrile in MCM-41 (C18) is 7.0 kJ mol(-1) compared to the bulk value of 12.7 kJ mol(-1). The relaxation times for tumbling rotational diffusion of cc-acetonitrile are similar to bulk values.     

Nanostructure protein repellant amphiphilic copolymer coatings with optimized surface energy by Inductively Excited Low Pressure Plasma

Statistically designed amphiphilic copolymer coatings were deposited onto Thermanox, Si wafer, and quartz crystal microbalance (QCM) substrates via Plasma Enhanced Chemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl acrylate and diethylene glycol vinyl ether in an Inductively Excited Low Pressure Plasma reactor. Plasma deposited amphiphilic coatings were characterized by Field Emission Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, Atomic Force Microscopy, and Water Contact Angle techniques. The surface energy of the coatings can be adjusted between 12 and 70 mJ/m(2). The roughness of the coatings can be tailored depending on the plasma mode used. A very smooth coating was deposited with a CW (continuous wave) power, whereas a rougher surface with R(a) in the range of 2 to 12 nm was deposited with the PW (pulsed wave) mode. The nanometer scale roughness of amphiphilic PFDA-co-DEGVE coatings was found to be in the range of the size of the two proteins namely BSA and lysozyme used to examine for the antifouling properties of the surfaces. The results show that the statistically designed surfaces, presenting a surface energy around 25 mJ/m(2), present no adhesion with respect to both proteins measured by QCM.