Investigation of thin films formed from liposome suspensions on quartz substrate

The stability of thin wetting films formed from 0.15 M NaCl solutions containing small unilamellar dimyristoylphosphatidylcholine (DMPC) vesicles of different concentrations on quartz surface has been investigated by the microinterferometric method. The intensity of monochromatic light reflected from both film surfaces has been recorded as a function of the time of film thinning. Two temperatures were used in the experiments (20 and 35 degrees C). Films containing 10(-3), 5x10(-3) and 10(-2) mg/ml DMPC were unstable and ruptured, while films with 10(-1) and 1 mg/ml DMPC were stable. Film stability was explained on the basis of hydrophobic interactions. Film thickness dependence on time was calculated. The kinetics of film thinning did not obey Reynolds equation and a linearization was observed in co-ordinates ln(h) as a function of time. This phenomenon was explained by a non-homogeneous thinning process, which might be due to the existence of some areas of different structure of the DMPC adsorption layers.     

Foam films stabilized with alpha olefin sulfonate (AOS)

Alpha olefin sulfonate (AOS) surfactants have shown outstanding detergency, lower adsorption on porous rocks, high compatibility with hard water and good wetting and foaming properties. These properties make AOS an excellent candidate for foam applications in enhanced oil recovery. This paper summarizes the basic properties of foam films stabilized by an AOS surfactant. The foam film thickness and contact angle between the film and its meniscus were measured as a function of NaCl and AOS concentrations. The critical AOS concentration for formation of stable films was obtained. The critical NaCl concentration for formation of stable Newton black films was found. The dependence of the film thickness on the NaCl concentration was compared to the same dependence of the contact angle experiments. With increasing NaCl concentration the film thickness decreases gradually while the contact angle (and, respectively the free energy of film formation) increases, in accordance with the classical DLVO theory.The surface tension isotherms of the AOS solutions were measured at different NaCl concentrations. They coincide on a single curve when plotted as a function of mean ionic activity product. Our data imply that the adsorption of AOS is independent of NaCl concentration at a given mean ionic activity.     

Thin wetting films from aqueous electrolyte solutions on SiC/Si wafer

The stability and rupture of thin wetting films from aqueous NaCl or Na2SO4 solutions of different concentrations on silicon carbide were investigated. The flat surface of SiC was obtained by plasma-enhanced chemical vapor deposition (PE-CVD) on top of a silicon wafer. The microinterferometric method was used for measuring the film thickness with time. The light reflectance was calculated as a function of film thickness for the four-layer system: air/aqueous solution/SiC/Si wafer. The microinterferometric experiments showed that films from aqueous NaCl and Na2SO4 solutions with concentrations up to 0.01 M were stable independent of the pre-treatment of the substrate. The pre-treatment of the SiC surface was crucial for the wetting film stability at electrolyte concentrations greater than 0.01 M. The films were unstable and ruptured if SiC was washed with 5% hydrofluoric acid and concentrated sulfuric acid, while they were stable if washing was in sulfuric acid only, without immersing SiC in HF. The average equilibrium film thickness was determined as a function of electrolyte concentration. Measurements of the electrokinetic potential zeta were performed by electrophores of SiC powder in 0.001 M NaCl. It was shown that silicon carbide surface was negatively charged. The theory of heterocoagulation was used for the interpretation of the results. Besides the DLVO forces, the structural disjoining pressure (both positive and negative) has been included in the analysis.     

An experimental test of the fractal model for drainage of foam films

Drainage of foam films with different radii (50-150 μm), stabilized by hexathylene glycol dodecyl ether C(12)E(6) and in a presence of 0.024 M NaCl, were analyzed in the light of a recent dynamic fractal classification of [1]. The latter accounts for the effect of film surface corrugations developed during the film drainage. For simplicity, the film surface mobility is neglected since the presence of surfactants reduces dramatically the film surface velocity. The magnitude of surface non-homogeneities, caused by the film drainage, is accounted via a dynamic fractal dimension parameter α being spanned between zero and two. Depending on the α-value the film drains by different kinetic laws. For example, if the thin film is planar α=2 and it drains according to the Reynolds law; if α=1 the film contains an axisymmetric dimple causing faster drainage; if α=1/2 the film exhibits number of asymmetric dimples and the film drains even faster; finally if α=0 the film contains spatially uncorrelated domains causing the fastest possible drainage. The present analysis of experimental data suggests that the parameter α is inversely proportional to the film radius R and it is independent of the type and concentration of surfactants. A semi-empirical model for α is proposed, thus completing the generic dynamic fractal classification.     

Thermodynamic studies on thin liquid films. III: Miscibility in adsorbed films at film interfaces

Thermodynamic treatment of surfactant mixture was developed for the adsorption at interfaces of thin liquid films and applied to the study of the foam film stabilized by decyl methyl sulfoxide (DeMS) in the presence of NaCl. The total surface density of NaCl and DeMS and the mole fraction of DeMS in the adsorbed film at the film surface were numerically evaluated by applying thermodynamic equations to the film tension as a function of the total molality of NaCl and DeMS and the mole fraction of DeMS in the mixture. Miscibility of NaCl and DeMS at the film surface was clarified by a phase diagram of adsorption and compared with that at the meniscus adjacent to the foam film. Judging from a phase diagram of phase transition, the transition in the DeMS foam film between common black and Newton black films, observed in part II, is a negative azeotropic transformation caused by the attractive interaction between the head group of DeMS molecule and Na⁺ or Cl^– in the adsorbed film.     

Effects of surface morphology on the anchoring and electrooptical dynamics of confined nanoscale liquid crystalline films

The orientation and dynamics of two 40-nm thick films of 4-n-pentyl-4'-cyanobiphenyl (5CB), a nematic liquid crystal, have been studied using step-scan Fourier transform infrared spectroscopy (FTIR). The films are confined in nanocavities bounded by an interdigitated electrode array (IDA) patterned on a zinc selenide (ZnSe) substrate. The effects of the ZnSe surface morphology (specifically, two variations of nanometer-scale corrugations obtained by mechanical polishing) on the initial ordering and reorientation dynamics of the electric-field-induced Freedericksz transition are presented here. The interaction of the 5CB with ZnSe surfaces bearing a spicular corrugation induces a homeotropic (surface normal) alignment of the film confined in the cavity. Alternately, when ZnSe is polished to generate fine grooves along the surface, a planar alignment is promoted in the liquid crystalline film. Time-resolved FTIR studies that enable the direct measurement of the rate constants for the electric-field-induced orientation and thermal relaxation reveal that the dynamic transitions of the two film structures are significantly different. These measurements quantitatively demonstrate the strong effects of surface morphology on the anchoring, order, and dynamics of liquid crystalline thin films.     

Matrix-assisted pulsed laser evaporation of polyimide thin films and the XPS study

Compared with the traditional thin film techniques, the matrix-assisted pulsed laser evaporation (MAPLE) technique has many advantages in the deposition of polymer and organic thin films. It has a wide range of applications in many fields, such as non-linear optics, luminescent devices, electronics, various sensors. We have successfully deposited polyimide thin films by using the MAPLE technique. These films were characterized with XPS. The XPS spectra showed that the single-photon effect is ob-vious at low laser fluence and the chemical bonds will be broken, resulting in decomposition of the films. Contrarily, the single-photon effect will decrease and the multi-photon effect and the photothermal effect will increase at high laser fluence, resulting in the protection of the structure of the polyimide thin films and the obvious decrease in decomposition. High laser fluence is more suitable for the deposition of polymer and organic thin films than low laser fluence.     

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.     

Thermal Decomposition Studies of Organoplatinum Films

 This study examines the thermal decomposition of 1,5-cyclooctadiene platinum (II) chloride organometallic films, deposited by thermal evaporation. The thin film samples were annealed both in air and hydrogen with well-controlled temperature regimes. After annealing, the decomposed thin films were examined by AFM and STM scanning probe, XPS and TEM microbeam analytical techniques. The experimental results confirm that the thermal decomposition products on silicon substrates are composed predominantly of metallic platinum. Annealing in hydrogen can reduce substantially the decomposition temperature of the material from around 250 to 160 °C but the surface morphology of the decomposed films is significantly different to those annealed in air. The metallic nature of the thermally decomposed films was confirmed by bonding configuration recognition, electronic property probing and microstructure analysis.     

Preparation of TiO2 thin films using water-soluble titanium complexes and their photoinduced properties

Titanium dioxide thin films were prepared by using four water-soluble titanium complexes of titanium-lactate, tartalate, malate and salicylate complex solutions. The crystalline phases detected in the films were anatase. The surface microstructures of the four film samples were different in their grain sizes. Photocatalytic decomposition activity of the four films was almost the same, but their photoinduced hydrophilicities were different. The film prepared using titanium-salicylate complex exhibited lower hydrophilic conversion rate than the other films. Grain size and stress yielded to the film are considered to be important factors on the photoinduced hydrophilicity.     

Bimodal swelling responses in microgel thin films

A series of studies on microgel thin films is described, wherein quartz crystal microgravimetry (QCM), surface plasmon resonance (SPR), and atomic force microscopy (AFM) have been used to probe the properties of microstructured polymer thin films as a function of film architecture and solution pH. Thin films composed of pNIPAm-co-AAc microgels were constructed by using spin-coating layer-by-layer (scLbL) assembly with poly(allylamine hydrochloride) (PAH) as a polycationic "glue". Our findings suggest that the interaction between the negatively charged microgels and the positively charged PAH has a significant impact on the pH responsivity of the film. These effects are observable in both the optical and mechanical behaviors of the films. The most significant changes in behavior are observed when the motional resistance of a quartz oscillator is monitored via QCM experiments. Slight changes to the film architecture and alternating the pH of the environment significantly changes the QCM and SPR responses, suggesting a pH-dependent swelling that is dependent on both particle swelling and polyelectrolyte de-complexation. Together, these studies allow for a deeper understanding of the morphological changes that take place in environmentally responsive microgel-based thin films.     

Efficient Sensing of Explosives by Using Fluorescent Nonporous Films of Oligophenyleneethynylene Derivatives Thanks to Optimal Structure Orientation and Exciton Migration

The fluorescence of thin films of a diimine‐substituted phenyleneethynylene compound can be efficiently quenched by nitroaromatic vapors, which is not the case for the unsubstituted parent compound. Thin‐film porosity is usually considered to be an essential factor for efficient quenching, but in the present case the origin of the quenching is completely different, as both films are nonporous and hermetic to 2,4‐dinitrotoluene (DNT) molecules. The molecular organization in the two crystallized thin films offers a low level of π stacking for both compounds, but the orientation of the phenylenethynylene fluorophore differs markedly with respect to the surface of the films. For the substituted compound, the fluorophore is almost parallel to the surface, thus making it readily available to molecules of a nitroaromatic quencher. This rationale is also observed in the case of a related compound bearing methoxy side chains instead of the long octyloxy moieties. Fluorescence‐lifetime experiments show that the efficient quenching process in the nonporous crystallized films of the substituted compound is due to a fast (<70 ps) diffusion of excitons from the bulk of the film toward the surface where they are quenched, thus providing evidence of antenna effects.     

Photoelectron spectroscopic studies of the formation of hydroxyapatite films on 316L stainless steel pretreated with etidronic acid

The valence band and core‐level X‐ray photoelectron spectroscopy was used to probe hydroxyapatite films formed on the surface of stainless steel. These films formed on steel may find application in medical implants. The key to the successful adhesion of the hydroxyapatite films is shown to be the initial formation of a thin, oxide‐free etidronate film on the metal. It was not found possible to prepare the hydroxyapatite films directly on the metal surfaces. Since hydroxyapatite is a key component of bone and teeth, it is likely that the coated metals will have desirable biocompatible properties. The hydroxyapatite film was exposed to air, water, and 1M sodium chloride solution as representative components of the environment of the film in the human body, and these exposures led to no detectable decomposition of the film. The thin hydroxyapatite and etidronate film on the metal show differential charging effects that caused a doubling of the peaks in some core level spectra. The valence band spectra proved especially valuable in the identification of the surface chemistry of the films, and these spectra were interpreted by comparing the experimental spectra with spectra calculated using band structure calculations which showed good agreement with experiment. The calculated spectrum of etidronic acid was found to be significantly different to that of etidronate. Copyright © 2012 John Wiley & Sons, Ltd.     

Thin liquid films containing micelles or nanoparticles

The stratification/microstructure formation inside suspended thin liquid films containing micelles or other nanoparticles is reviewed with the aim of clarifying some key issues and suggesting unresolved questions requiring further investigation. New experiments reveal that the micellar layer thinning phenomenon is a reversible process in films formed from non-ionic micellar solutions. The important factors contributing to the correlation between the ordered microstructure formation that leads to a high structural stabilization force in a single free suspended film and the stability of macrodispersions (such as foams and emulsions and particle suspensions) are also discussed.     

Foam films stabilized by dodecyl maltoside. 1. Film thickness and free energy of film formation

Foam films stabilized by a sugar-based nonionic surfactant, beta-dodecyl maltoside, are investigated. The film thickness and the film contact angle (which is formed at the transition between the film and the bulk solution) are measured as a function of NaCl concentration, surfactant concentration, and temperature. The film thickness measurements provide information about the balance of the surface forces in the film whereas the contact angle measurements provide information about the specific film interaction free energy. The use of the glass ring cell and the thin film pressure balance methods enables studies under a large variety of conditions. Thick foam films are formed at low electrolyte concentration. The film thickness decreases (respectively the absolute value of the interaction film free energy increases) with the increase of the electrolyte concentration according to the classical DLVO theory. This indicates the existence of a repulsive double layer electrostatic component of the disjoining pressure. An electrostatic double layer potential of 16 mV was calculated from the data. A decrease of the film thickness on increase of the surfactant concentration in the solution is observed. The results are interpreted on the basis of the assumption that the surface double layer potential originates in the adsorption of hydroxyl ions at the film surfaces. These ions are expelled from the surface at higher surfactant concentration.     

Influence of NaCl on the behavior of PEO-PPO-PEO triblock copolymers in solution, at interfaces, and in asymmetric liquid films

The solution behavior of the polymeric surfactant Pluronic F127 (PEO(99)PPO(65)PEO(99)) and its adsorption behavior on aqueous-silica and aqueous-air interfaces, as well as the disjoining pressure isotherms of asymmetric films (silica/aqueous film/air) containing F127, are studied. The interfacial properties of adsorbed F127 layers (the adsorbed amount Gamma and the thickness h) as well as the aqueous wetting film properties [film thickness (h) and refractive indexes] were studied via ellipsometry. The solution properties of F127 were investigated using surface tensiometry and light scattering. The interactions between the air-water and silica-water interfaces were measured with a thin film pressure balance technique (TFB) and interpreted in terms of disjoining pressure as a function of the film thickness. The relations between the behaviors of the asymmetric films, adsorption at aqueous air, and aqueous silica interfaces and the solution behavior of the polymeric surfactant are discussed. Special attention is paid to the influence of the concentrations of F127 and NaCl. Addition of electrolyte lowers the critical micelle concentration, diminishes adsorption on silica, and increases the thickness of the asymmetric film.     

Surface morphology and biological activity of protein thin films produced by electrospray deposition

Protein thin films were prepared by the electrospray deposition (ESD) method from aqueous solutions of alpha-lactalbumin (alpha-LA) at different concentrations, and their surface morphologies and biological activities were characterized. The surface morphologies of the deposited films were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The SEM and AFM images showed that the film surfaces had a fine porous structure, in which the pore diameters ranged from 40 to 600 nm. The biological activities of the cross-linked protein films were tested by the mechanochemical method. The response to calcium ion (Ca(2+)) demonstrated that the biological activity of the films was preserved. These results indicate that the ESD method is potentially useful for the fabrication of active protein thin films. The freestanding protein thin films prepared by ESD and postdeposition cross-linking provide novel options for protein-based biomaterials.     

Effect of fullerene coating on silicon thin film anodes for lithium rechargeable batteries

To improve the electrochemical performances of Si thin film anodes for lithium rechargeable batteries, fullerene thin films are prepared by plasma-assisted evaporation methods to be used as coating materials. Analyses via Raman and X-ray photoelectron spectroscopy indicate that amorphous polymeric films originated from fullerene are formed on the surface of the silicon thin film. The electrochemical performance of these fullerene-coated silicon thin film as an anode material for rechargeable lithium batteries has been investigated by cyclic voltammetry, charge/discharge tests, and electrochemical impedance spectroscopy. The fullerene-coated Si thin films demonstrated a high specific capacity of above 3,000 mAh g⁻¹ as well as good capacity retention for 40 cycles. In comparison with bare silicon anodes, the fullerene-coated silicon thin film showed superior and stable cycle performance which can be attributed to the fullerene coating layer which enhances the Li-ion kinetic property at the electrode/electrolyte interface.     

Anchoring and electro-optical dynamics of thin liquid crystalline films in a polyimide cell: experiment and theory

The surface-dependent anchoring and electro-optical (EO) dynamics of thin liquid crystalline films have been examined using Fourier transform infrared spectroscopy. A simple nematic liquid crystal, 4-n-pentyl-4'-cyanobiphenyl (5CB), is confined as 40, 50, and 390 nm thick films in nanocavities defined by gold interdigitated electrode arrays (IDEAs) patterned on polyimide-coated zinc selenide (ZnSe) substrates [Noble et al., J. Am. Chem. Soc. 124, 15020 (2002)]. New strategies for controlling the anchoring interactions and EO dynamics are explored based on coating a ZnSe surface with an organic polyimide layer in order to both planarize the substrate and induce a planar alignment of the liquid crystalline film. The polyimide layer can be further treated so as to induce a strong alignment of the nematic director along a direction parallel to the electrode digits of the IDEA. Step-scan time-resolved spectroscopy measurements were made to determine the rate constants for the electric-field-induced orientation and thermal relaxation of the 5CB films. In an alternate set of experiments, uncoated ZnSe substrates were polished unidirectionally to produce a grooved surface presenting nanometer-scale corrugations. The dynamical rate constants measured for several nanoscale film thicknesses and equilibrium organizations of the director in these planar alignments show marked sensitivities. The orientation rates are found to vary strongly with both the magnitude of the applied potential and the initial anisotropy of the alignment of the director within the IDEA. The relaxation rates do not vary in this same way. The marked variations seen in EO dynamics can be accounted for by a simple coarse-grained dynamical model.     

旋涂水溶液前驱体制备氧化锌薄膜及其性质

通过旋涂法, 采用Zn(OAc)2·2H2O和聚环氧乙烷(PEO)的水溶液为前驱体在不同的热处理温度下制备了ZnO薄膜. PEO的加入增加了溶液的成膜性, 其较低的热分解温度有利于制得纯净的ZnO薄膜. 文中考察了在不同热处理温度下制备的ZnO薄膜的形貌、结晶性、带隙(Eg)以及电导性. 原子力显微镜(AFM)测试表明在热处理温度为400、450和500 ℃制备的ZnO薄膜的粗糙度均方根值分别为3.3、2.7和3.6 nm. 采用透射电子显微镜(TEM)测试发现ZnO薄膜中含有大量纳晶粒子. 通过测试ZnO薄膜的UV-Vis吸收光谱, 根据薄膜位于373 nm处的吸收带边计算得到ZnO的带隙为3.3 eV. 通过对薄膜的电流-电压(I-V)曲线的测试计算得到在热处理温度为400、450和500 ℃制备的ZnO薄膜的电阻率分别为3.3×109、2.7×109和6.6×109 Ω·cm. 450 ℃时制备的ZnO薄膜的电阻率最小, 主要是由于较高的热处理温度有利于提高薄膜的纯度、密度和吸附氧. 而纯度较高、密度较大的薄膜电阻率比较小; 吸附氧含量增加, 晶界势垒增大, 电阻率增大. 因此在纯度和吸附氧的双重作用下450 ℃时制备的ZnO薄膜的电阻率最小, 而500 ℃时制备的ZnO薄膜的电阻率最大.