The Molecular Spreading of Nonpolar Perfluoropolyether Films on Amorphous Carbon Surfaces

The spreading mechanism of nonpolar perfluoropolyether films on carbon surfaces is examined in the mesoscopic regime, including both submonolayer and multilayer films. For the submonolayer film, adsorption-desorption is a main mechanism for spreading, and the surface diffusion coefficients increase as the film thickness increases. The driving force for the spreading in the submonolayer regime is the gradient of the disjoining pressure, which is described by the two-dimensional virial equation. For the multilayer film regime, the spreading characteristics are determined by the molecular weight and the disjoining pressure gradient, which is assumed to be purely van der Waals in nature. We adopt a partial slip boundary condition to analyze the multilayer film, which qualitatively explains the dependence of the surface diffusion coefficient on film thickness. Copyright 2000 Academic Press.     

In Vitro Degradation of Poly(lactic-co2-glycolic) Acid Random Copolymers

We have investigated the in vitro degradation of poly(lactic-co-glycolic) acid copolymer with a lactic to glycolic ratio of 65/35. The degradation studies were performed on solvent-cast films of controlled thickness and shape. The samples were then incubated at 37 °C in phosphate buffered saline solution. The degradation was followed using potentiometry, light microscopy, gravimetry, gel permeation chromatography and differential scanning calorimetry. Water was found to diffuse inside the film as soon as the sample was placed in the degradation media. Wrinkles formed on the upper layer while degradation took place via chain scission in the bulk of the film. After 10 days, this led to the creation of a vesicle where liquid low molecular weight oligomers were trapped inside a thin film of high molecular weight polymer. This thin film acted as a membrane allowing only low molecular weight compounds to diffuse out of the film.     

Diffraction grating in noncrosslinked polymers

The diffraction efficiency and morphology of the transmission modes of holographic polymer dispersed liquid crystals were studied with respect to the molecular structure of poly(urethane acrylate) (PUA), the film (polymer/liquid crystal) and resin (oligomer/monomer) compositions, and the cell thickness. PUA, based on N‐vinylpyrrolidone and ethyl hexyl acrylate, with low‐molecular‐weight poly(propylene glycol) at a low oligomer content, showed high diffraction efficiency. The results were interpreted in terms of the monomer reactivity and polymer elasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 613–620, 2004     

Instability, dynamics, and morphology of thin slipping films

Based on the linear stability and nonlinear simulations, we show that the surface instability, dynamics, and morphology of supported thin liquid films are profoundly altered by the presence of slippage on the substrate. A general dispersion equation for flow in slipping thin films is derived and simplified to identify three different regimes of slippage (weak, moderate, and strong) and obtain the length and time scales of instability in them. For illustration, the ubiquitous van der Waals interactions have been employed. Different regimes of slip-flow can be predicted based on a nondimensional parameter, xi, which is a function of slip length, film thickness, intermolecular potential, and interfacial tension. Two distinct transitions from weak to moderate slip and from moderate to strong slip occur at xiT1 approximately 0.01 and xiT2 approximately 500, respectively. More specifically, a decrease in film thickness causes transitions from weak to moderate to strong slip regime. Even a weak slippage causes faster breakup of a thin film, whereas slippage beyond a transition value (slip length, bT1) increases the length scale of instability and reduces the number density of holes compared to the nonslipping case. Strong slippage produces holes faster, and the holes are fewer in number and have less developed rims. The exponents for the length scale (lambdam infinity h0n; h0 is film thickness) and time scale of instability (tr infinity h0m) change nonmonotonically with slippage (for nonretarded van der Waals instability, n E (1.25, 2), m E (3, 6)). Retardation in van der Waals potential increases the exponents (n E (1.5, 2.5), m E (5, 8)). The initial stage of evolution of a slipping film, simulated based on nonlinear equations, follows the length scale and time scale of instability, close to the prediction of linear analysis. It is hoped that the present analysis will help in better interpretation of thin film experiments, in estimation of slippage, and in the determination of intermolecular forces from the length and time scales of the instability.     

Emulsion polymerization. II. Review of experimental data in the context of the revised Smith-Ewart theory

Tables are presented for convenient calculation of the basic parameters of the revised Smith-Ewart theory. For the methyl methacrylate (MMA)/sodium lauryl sulfate (SLS)/K₂S₂O₈, and for the styrene/SLS/K₂S₂O₈ reaction mixtures parameters are presented from which the absolute values of the following quantities can be conveniently calculated for any temperature, soap, and initiator concentration: particle number, particle radius, conversion where particle nucleation stops, rate and molecular weight in interval II, the interval after completion of particle nucleation and before the disappearance of monomer droplets. The theoretical predictions are compared to new experimental data and to those from the literature. The available data confirm the theoretical prediction that particle nucleation stops after a very small amount of polymer is formed, of the order of 0.01 cc. polymer/cc. water in most recipes. The theory and experiments are in good qualitative agreement for the conversion rate prior to completion of particle formation: the conversion rate rises with time and, when particle nucleation stops, it levels off. Excellent quantitative agreement can be obtained between theoretical and experimental particle size values. In the experiments of this laboratory the SLS concentration was varied 60-fold, the K₂S₂O₈ concentration was varied 140-fold and the difference between theoretical and experimental poly(MMA) particle radii was always less than about 20%. Similar good agreement was obtained for polystyrene over the temperature range 30–90°C. Some polystyrene data from the literature with carboxylic soaps give just as good fit as the data with SLS of this laboratory. The predicted proportionality between particle number and the product of 0.6 power of soap concentration and of 0.4 power of initiator concentration was observed for several monomers. The theoretical predictions for the rate and molecular weight obtained in interval II are valid only for relatively low initiator and high soap recipes. For recipes for MMA and styrene the rate data are in good agreement with those calculated from the theory. The theory also correctly predicts the order of magnitude of the experimental molecular weights. For several monomers the rate and molecular weight vary with initiator and soap concentrations in a manner close to theoretical predictions.     

Formation of n-alkane layers at the vapor/water interface

We present a study on the initial wetting behaviors of two low molecular weight alkanes, heptane and octane, at the vapor/water interface using both neutron and X-ray reflectometry. Combined X-ray and neutron reflectivity studies data showed that a uniform film, which has never been reported, was formed continuously at 25 degrees C. As the adsorptive deposition continued, each adsorbed film was saturated at a specific equilibrium thickness: 48 and 36 A for deuterated heptane and octane, respectively, and 21 A for hydrogenated octane. The thickness of the adsorbed layer measured by neutron reflectivity is in agreement with that measured using X-ray reflectivity. Our observations of continuous and saturated adsorption behaviors are analyzed qualitatively using a kinetic adsorption model.     

Influence of the polyelectrolyte molecular weight on exponentially growing multilayer films in the linear regime

Alternated deposition of polyanions and polycations on a charged solid substrate leads to the buildup of polyelectrolyte multilayer (PEM) films. Two types of PEM films were reported in the literature: films whose thickness increases linearly and films whose thickness increases exponentially with the number of deposition steps. However, it was recently found that, for exponentially growing films, the exponential increase of the film thickness takes place only during the initially deposited pairs of layers and is then followed by a linear increase. In this study, we investigate the growth process of hyaluronic acid/poly(L-lysine) (HA/PLL) and poly(L-glutamic acid)/poly(allylamine) (PGA/PAH) films, two films whose growth is initially exponential, when the growth process enters the linear regime. We focus, in particular, on the influence of the molecular weight (Mw) of the polyelectrolytes. For both systems, we find that the film thickness increment per polyanion/polycation deposition step in the linear growth regime is fairly independent of the molecular weights of the polyelectrolytes. We also find that when the (HA/PLL)n films are constructed with low molecular weight PLL, these chains can diffuse into the entire film during each buildup cycle, even for very thick films, whereas the PLL diffusion of high molecular weight chains is restricted to the upper part of the film. Our results lead to refinement of the buildup mechanism model, introduced previously for the exponentially growing films, which is based on the existence of three zones over the entire film thickness. The mechanism no longer needs all the "in" and "out" diffusing polyanions or polycations to be involved in the buildup process to explain the linear growth regime but merely relies on the interaction between the polyelectrolytes with an upper zone of the film. This zone is constituted of polyanion/polycation complexes which are "loosely bound" and rich in the polyelectrolyte deposited during the former deposition step.     

Ligand-receptor interactions in tethered polymer layers

The binding of small proteins to ligands that are attached to the free ends of polymers tethered to a planar surface is studied using a molecular theory. The effects of changing the intrinsic binding equilibrium constant of the ligand-receptor pair, the polymer surface coverage, the polymer molecular weight, and the protein size are studied. The results are also compared with the case where ligands are directly attached to the surface without a polymer acting as a spacer. We found that within the biological range of binding constants the protein adsorption is enhanced by the presence of the polymer spacers. There is always an optimal surface coverage for which ligand-receptor binding is a maximum. This maximum increases as the binding energy and/or the polymer molecular weight increase. The presence of the maximum is due to the ability of the polymer-bound proteins to form a thick layer by dispersing the ligands in space to optimize binding and minimize lateral repulsions. The fraction of bound receptors is unity for a very small surface coverage of ligands. The very sharp decrease in the fraction of bound ligand-receptor pairs with surface coverage depends on the polymer spacer chain length. We found that the binding of proteins is reduced as the size of the protein increases. The orientation of the bound proteins can be manipulated by proper choice of the grafted layer conditions. At high polymer surface coverage the bound proteins are predominantly perpendicular to the surface, while at low surface coverage there is a more random distribution of orientations. To avoid nonspecific adsorption on the surface, we studied the case where the surface is covered by a mixture of a relatively high molecular weight polymer with a ligand attached to its free end and a low molecular weight polymer without ligand. These systems present a maximum in the binding of proteins, which is of the same magnitude as when only the long polymer-ligand is present. Moreover, when the total surface coverage in the mixed layers of polymers is high enough, nonspecific adsorption of the proteins on the surface is suppressed. The use of the presented theoretical results for the design of surface modifiers with tailored abilities for specific binding of proteins and optimal nonfouling capabilities is discussed.     

Direct measurement of molecular motion in freestanding polystyrene thin films

An optical photobleaching technique has been used to measure the reorientation of dilute probes in freestanding polystyrene films as thin as 14 nm. Temperature-ramping and isothermal anisotropy measurements reveal the existence of two subsets of probe molecules with different dynamics. While the slow subset shows bulk-like dynamics, the more mobile subset reorients within a few hundred seconds even at T(g,DSC) - 25 K (T(g,DSC) is the glass transition temperature of bulk polystyrene). At T(g,DSC) - 5 K, the mobility of these two subsets differs by 4 orders of magnitude. These data are interpreted as indicating the presence of a high-mobility layer at the film surface whose thickness is independent of polymer molecular weight and total film thickness. The thickness of the mobile surface layer increases with temperature and equals 7 nm at T(g,DSC).     

Effect of poly(ethylene oxide)-silane graft molecular weight on the colloidal properties of iron oxide nanoparticles for biomedical applications

The size, charge, and stability of colloidal suspensions of magnetic nanoparticles with narrow size distribution and grafted with poly(ethylene glycol)-silane of different molecular weights were studied in water, biological buffers, and cell culture media. X-ray photoelectron spectroscopy provided information on the chemical nature of the nanoparticle surface, indicating the particle surfaces consisted of a mixture of amine groups and grafted polymer. The results indicate that the exposure of the amine groups on the surface decreased as the molecular weight of the polymer increased. The hydrodynamic diameters correlated with PEG graft molecular weight and were in agreement with a distributed density model for the thickness of a polymer shell end-grafted to a particle core. This indicates that the particles obtained consist of single iron oxide cores coated with a polymer brush. Particle surface charge and hydrodynamic diameter were measured as a function of pH, ionic strength, and in biological buffers and cell culture media. DLVO theory was used to analyze the particle stability considering electrostatic, magnetic, steric, and van der Waals interactions. Experimental results and colloidal stability theory indicated that stability changes from electrostatically mediated for a graft molecular weight of 750 g/mol to sterically mediated at molecular weights of 1000 g/mol and above. These results indicate that a graft molecular weight above 1000 g/mol is needed to produce particles that are stable in a wide range of pH and ionic strength, and in cell culture media.     

Layer-by-layer assembly of partially sulfonated isotactic polystyrene with poly(vinylamine)

The stereoregular synthetic polymer isotactic polystyrene bearing partially sulfonated groups (SiPS) was used as a layer-by-layer assembled thin film for the first time. When a low molecular weight compound was employed as the pair for the alternative layer-by-layer (LbL) assembly, the frequency shift was very small using quartz crystal microbalance (QCM) analysis, whereas poly(vinylamine) (PVAm) formed an effective pair for the construction of LbL films with SiPS. When it was neutralized, SiPS was not assembled, probably due to the loss of effective polymer-polymer interactions. The ionic strength conditions revealed a slight difference of the assembly behavior on the isotactic polymer as compared to the atactic one. The assembled LbL film showed the same peaks over the range from 1141 to 1227 cm(-1) and 700 cm(-1) in the FT-IR/ATR spectra as the bulk complex of SiPS/PVAm, and the thickness on one side was calculated at 76 nm by QCM analysis. The surface roughness of the film was also observed by AFM.     

Boundary viscosity of polydimethylsiloxane liquids and their binary mixtures

A systematic study is made of the boundary viscosity of a number of polydimethylsiloxane liquids (PMS) of molecular weights ranging from 1,000 to 40,000 by the blow-off method, film thicknesses being measured by a modulation-polarimetric (elliposmetric) precedure. It is established experimentally that the viscosity of the liquids studied is not the same throughout the thickness of the boundary later.

PMS applied to glass and steel substrates retain their bulk viscosity values down to a layer thickness of ca. 150–200 Å, below which the viscosity increases slightly. On further decrease of the distance to 10–15 Å from the substrate, the viscosity becomes anomalously low, amounting to about 10–20 % of the bulk value. The existence of a layer of anomalously low viscosity may be attributed to orientation of the PMS molecules in the plane of the substrate, and hence, to the ease with which these oriented layers slip relative to one another.

When studying the boundary viscosity of binary mixtures of PMS of different molecular weights, boundary phases of elevated viscosity were found to exist at a distance of 15–30 Å from the substrate. This phenomenon may be attributed to a change in concentration of the mixture at the solid surface i.e., to an increase in content of the component with the higher molecular weight in the wall-adjacent layer.     

Spontaneous pattern formation by dip coating of colloidal suspensions on homogeneous surfaces

We study the slow withdrawal of a partially wet vertical plate at velocity U from a suspension of well-wet particles. Periodic horizontal striped assemblies form spontaneously at the three-phase contact line on energetically uniform surfaces. Stripe width and spacing depend on the withdrawal velocity U relative to a transition velocity Ut. Thick stripes separated by large spaces form for UUt, thin stripes separated by small spaces form. The stripe spacing is reduced by an order of magnitude and varies weakly with U until a maximum velocity is reached at which the stripes fail to form. A partially wet surface can entrain a meniscus. For UUt, we infer that a film of thickness h is entrained above the meniscus. When h is smaller than the particle diameter D, particles aggregate where the entrained film thickens to match up to the wetting meniscus. When an entrained particle becomes exposed to air by evaporation, it becomes the new pinning site from which the next film is entrained. The film thickness h increases with U; at some velocity, h becomes comparable to D. Particles flow into the film and deposit there in a disordered manner. A diagram summarizing particle deposition is developed as a function of D, U, and h.     

Crystalline morphology evolution in PCL thin films

The transition of crystalline morphology is revealed in poly(?‐caprolactone) (PCL) thin films as the polymer film thickness changes from hundreds of nanometers to several nanometers. The PCL can crystallize into spherulites, dense‐branching morphology (DBM), or dendrites, depending on the polymer film thickness. It was found that when the polymer film thickness approaches 2Rg (radius of gyration of polymer), there is a remarkable change in crystalline morphology. Under this condition, the polymer crystallization is a diffusion‐controlled process. When the value of polymer film thickness closes to Rg, PCL cannot crystallize, and a dewetting phenomenon will take place. Moreover, polymer morphology can be controlled by varying supercooling. The effect of molecular weight on polymer morphology has been investigated. The main factors that affected pattern formation in nonequilibrium crystallization are also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1303–1309, 2005     

Landau-Levich menisci

As shown by Landau, Levich and Derjaguin, a plate withdrawn out of a wetting bath at low capillary numbers deforms the very top of the liquid reservoir. At this place, a dynamic meniscus forms, whose shape and curvature select the thickness of the film entrained by the plate. In this paper, we measure accurately the thickness of the entrained film by reflectometry, and characterize the dynamic meniscus, which is found to decay exponentially towards the film. We show how this shape is modified when reversing the motion: as a plate penetrates the bath, the dynamic meniscus can "buckle" and present a stationary wavy profile, which we discuss.     

Small-angle neutron scattering study of adsorbed pluronic tri-block copolymers on laponite

The adsorption of selected poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) tri-block copolymers on synthetic clay particles (laponite) has been investigated. The adsorbed amount and distribution of polymer was determined as a function of relative block composition and size, using the technique of contrast variation small-angle neutron scattering. The pluronic molecules appear to adsorb via a preferential segregation of hydrophobic PPO segments at the surface, with hydrophilic PEO segments dangling into solution. The effect of the PPO segments is substantial with large increases in adsorbed amount and layer thickness as the anchor fraction decreases/PEO chain length increases. This is in direct contrast to the behavior observed for PEO homopolymer adsorption (of much higher molecular weights) where the adsorbed amount and layer thickness are smaller and change little with molecular weight.     

Effect of tensile speed on mechanical characteristics of preliminary rolled polyethylene terephthalate films

The effect of tensile speed on the mechanical properties of amorphous polyethylene terephthalate films is studied. The films are oriented by rolling on laboratory rollers at room temperature. In the samples with the rolling degree of two, the subsequent tension with the velocity of 5 mm/min does not afford a neck. As the tensile speed increases to 500 mm/min, a neck results from instability of the deformation process, which is caused by the polymer heating. Upon high-speed tension, the temperature of the rolled samples exceeds the glass-transition point of polyethylene terephthalate. Despite the polymer heating, the rolling completely suppresses the formation of pores. The rolling leads to the delocalization of flow over the region of polymer transfer to the neck. While in the nonrolled films the flow occurs in the zone with the length on the order of the film thickness, after the rolling, the size of the flow zone increases, and the region with the length on the order of the film width is deformed.     

Effect of molecular weight on the exponential growth and morphology of hyaluronan/chitosan multilayers: a surface plasmon resonance spectroscopy and atomic force microscopy investigation

The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair.     

Measurements of dynamic interactions in thin films of polymer melts: The transition from simple to complex behavior

Two techniques are described for measuring the shear viscosities of thin liquid films confined between two surfaces. Both techniques employ the surface forces apparatus, which has already been used extensively to measure the static interactions between surfaces in liquids. With either of the new dynamic techniques, shear viscosities of the confined liquids can be measured as a function of film thickness with a precision of about 0.1 nm (1 Å). The techniques complement each other: one is used to best advantage at high shear rates, the other at low shear rates. Results are presented for measurements made on low-molecular-weight polymer melts of polybutadienes. At low shear rates, these results provide detailed information on the relation between polymer molecular weight, the conformation of polymer molecules at the surfaces, the intermolecular forces between the surfaces, and the location of the shear plane (plane of no-slip). At high shear rates, the results suggest the gradual evolution of non-Newtonian behavior in submicron liquid films.