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PubMed2004

Polystyrene thin films in CO(2).

In air, or vacuum environments, liquid polystyrene (PS) thin films (thickness, h<100 nm ) supported by SiOx /Si substrates are structurally metastable or unstable, depending on film thickness. They rupture and eventually form droplets on the SiOx /Si substrates (dewet) due to the influence of destabilizing long-ranged van der Waals dispersion forces. We used scanning force microscopy to examine the structural stability of liquid PS films in the thickness range 5 nm<h<100 nm in liquid and in supercritical carbon dioxide ( CO2 ) environments. All films in this thickness range were metastable; holes developed throughout the films and over time these holes grew, impinged, and eventually formed droplets. The rate of destabilization is controlled by three factors: film thickness, temperature, and CO2 pressure (which dictates CO2 volume fraction in the films). Calculations of the effective interface potentials suggest that the energy barrier for nucleation and growth of holes in CO2 is larger than that in air, and in the limit of vanishingly low PS volume fraction the films should be stable.

Journal Article↗
PubMed2004

Thickness dependence of structural relaxation in spin-cast, glassy polymer thin films.

The isothermal structural relaxation of glassy, spin-cast polymer thin films has been investigated. Specifically, the thickness h of freshly cast poly(methyl methacrylate) thin films was measured over time using spectroscopic ellipsometry. The spin-cast films exhibit a gradual decrease in thickness, which is attributed to structural relaxation of the glass combined with simultaneous solvent loss. In all cases, h was found to be greater than the equilibrium thickness h(infinity) , which is obtained by cooling slowly from the melt. It is observed that both the rate of the volume relaxation and the fractional departure from h(infinity) (referred to as delta(0) ) increase with increasing film thickness. In the limit of very thin films, the initial h is close to h(infinity) , and delta(0) is small, whereas in thick films (>500 nm) , a plateau value of delta(0) of 0.16 is observed, which is close to the volume fraction of the solvent at the vitrification point. This dependence of delta(0) on thickness is observed regardless of the substrate, polymer molecular weight, or angular velocity during spin casting. Enhanced mobility near film surfaces could be leading to greater relaxation in thinner films prior to, and immediately after, the vitrification of the polymer during the deposition process.

Journal Article↗
PubMed2005

Hole growth in freely standing polystyrene films probed using a differential pressure experiment.

We have probed the whole chain mobility of polymer molecules confined to freely standing films by measuring the flow of gas through holes growing in the films at elevated temperatures using a differential pressure experiment. Freely standing polystyrene films were measured for the temperature range 92 degrees C<T<105 degrees C for films with two different molecular weights Mw=717 x 10(3) and 2240 x 10(3) , with thicknesses 51 nm<h<97 nm . This range of film thicknesses is of particular interest because large reductions in the glass transition temperature Tg have been measured previously for freely standing PS films in this thickness range. We find that hole formation and growth, and therefore substantial chain mobility, does not occur until temperatures close to the bulk value of the glass transition temperature T(bulk)g. The characteristic growth times tau for the thinnest films, which have reduced values of Tg, are not substantially less than those for thicker films, and we find that these small differences in tau can be understood in terms of the bulk phenomenon of shear thinning. We also show that the viscosity at the edge of the hole inferred from the characteristic growth times obtained in this and previous studies exhibit shear thinning with reduced shear strain rates beta that span twelve orders of magnitude.

Journal Article↗
PubMed2003

Free surfaces cause reductions in the glass transition temperature of thin polystyrene films.

The effect of free surfaces on the glass transition temperature (T(g)) of thin polystyrene films was studied. Measurements were performed on films (8 nm<h<290 nm) with one free surface and on films capped with a 5 nm thick metal layer (no free surfaces). Potential problems with evaporative deposition were eliminated by studying samples made of two supported films placed with their free surfaces in contact and annealed. Uncapped films displayed reduced T(g) values for h less, similar 40 nm while all "properly" capped films exhibited a T(g) value the same as that of the bulk polymer (370+/-1 K). When the free surface was restored, the measured T(g) values the same as those of uncapped films of the same thickness. These results show that free surfaces are crucial for observing T(g) reductions in thin polymer films and address the role of the sample preparation history.

Journal Article↗
PubMed2005

Chain entanglement in thin freestanding polymer films.

When a thin glassy film is strained uniaxially, a shear deformation zone (SDZ) can be observed. The ratio of the thickness of the SDZ to that of the undeformed film is related to the maximum extension ratio, lambda, which depends on the entanglement molecular weight, M(e). We have measured lambda as a function of film thickness in strained freestanding films of polystyrene as a probe of M(e) in confinement. It is found that thin films stretch further than thick films before failure, consistent with the interpretation that polymers in thin films are less entangled than bulk polymers, thus the effective value of M(e) in thin films is significantly larger than that of the bulk. Our results are well described by a conceptually simple model based on the probability of finding intermolecular entanglements near an interface.

Journal Article↗
PubMed2001

Gellan film as an implant for insulin delivery.

Gellan gum is an anionic polysaccharide produced by the aerobic fermentation of Pseudomonas elodea in batch culture. Gellan undergoes calcium-induced cross-linking to form a three-dimensional network, and this property makes it particularly attractive for the incorporation of biological moieties such as proteins. In this study, a procedure for the preparation of gellan films was developed and optimized, and the characteristics of these films were investigated. In addition, the effects of the concentration of each ingredient in gellan films and in vitro release behavior of fluorescein isothiocyanate dextran from these films was examined. This film device was implanted for insulin delivery in diabetic rats. The blood glucose levels of the diabetic rats implanted with insulin-loaded films were about half of those implanted with blank films, and this therapeutic effect of insulin could last for one week. Both in vitro and in vivo studies indicated that the gellan film could be an ideal candidate in the development of protein delivery systems.

Animals↗
PubMed2005

Fabrication and characterization of micromachined high-frequency tonpilz transducers derived by PZT thick films.

Miniaturized tonpilz transducers are potentially useful for ultrasonic imaging in the 10 to 100 MHz frequency range due to their higher efficiency and output capabilities. In this work, 4 to 10-microm thick piezoelectric thin films were used as the active element in the construction of miniaturized tonpilz structures. The tonpilz stack consisted of silver/lead zirconate titanate (PZT)/lanthanum nickelate (LaNiO3)/silicon on insulator (SOI) substrates. First, conductive LaNiO3 thin films, approximately 300 nm in thickness, were grown on SOI substrates by a metalorganic decomposition (MOD) method. The room temperature resistivity of the LaNiO3 was 6.5 x 10(-6) omega x m. Randomly oriented PZT (52/48) films up to 7-microm thick were then deposited using a sol-gel process on the LaNiO3-coated SOI substrates. The PZT films with LaNiO3 bottom electrodes showed good dielectric and ferroelectric properties. The relative dielectric permittivity (at 1 kHz) was about 1030. The remanent polarization of PZT films was larger than 26 microC/cm2. The effective transverse piezoelectric e31,f coefficient of PZT thick films was about -6.5 C/m2 when poled at -75 kV/cm for 15 minutes at room temperature. Enhanced piezoelectric properties were obtained on poling the PZT films at higher temperatures. A silver layer about 40-microm thick was prepared by silver powder dispersed in epoxy and deposited onto the PZT film to form the tail mass of the tonpilz structure. The top layers of this wafer were subsequently diced with a saw, and the structure was bonded to a second wafer. The original silicon carrier wafer was polished and etched using a Xenon difluoride (XeF2) etching system. The resulting structures showed good piezoelectric activity. This process flow should enable integration of the piezoelectric elements with drive/receive electronics.

Journal Article↗
PubMed1975

Adsorption of DNA molecules to different support films.

Protein-free adsorption of the DNA of the Escherichia coli bacteriophage T7 to carbon, collodion, aluminium-beryllium and aluminium films was studied. It was found that the appearance of DNA strands depended greatly upon the kind of support film used. Direct adsorption of DNA to aluminium-beryllium or aluminium films yielded specimens with 'thin and long' and 'thick and short' regions along the strand. Well extended, uncoiled and unaggregated DNA molecules were obtained only when DNA was adsorbed to carbon, collodion or mica in the presence of intercalating dyes such as ethidium bromide. Adsorption properties of the different films are well correlated with their surface charge. Aluminium-beryllium films carry a strong positive surface charge, aluminium films a weak positive charge and carbon films a weak negative charge. It is suggested that for the preparation of specimens by spontaneous adsorption of well extended and unaggregated strands it is necessary that the DNA molecule is stiffened by a ligand such as an intercalating dye, and that the charge on the surface of the support film is opposite to the charge of the macromolecule.

Adsorption↗
PubMed2001

Patient and provider attitudes toward commercial television film crews in the emergency department.

UNLABELLED: One of the most successful reality-based television shows is The Learning Channel's "Trauma-Life in the ER," in which patients are filmed prior to being consented and camera crews are intimately intertwined in resuscitations. OBJECTIVE: To assess provider and patient attitudes regarding privacy and satisfaction during filming. METHODS: This was a prospective survey of patients and providers working in an urban, county teaching emergency department (ED). Scores of visual analog scales (VASs) for satisfaction, privacy, and willingness to return to the ED were accessed. RESULTS: Eighty patients, 39 physicians and 39 nurses, were interviewed. On a 10-cm VAS where 0 = no invasion of patient privacy and 10 = extreme privacy invasion, the mean (+/-SD) rating by physicians was 5.4 (+/-2.6), by nurses was 4.9 (+/-3.1), and by patients was 2.3 (+/-3.2). There was no significant difference between physician and nurse ratings (p = 0.69), but patients rated invasion of privacy significantly lower (p < 0.0001). Filmed patients rated significantly higher invasion of privacy (3.8 +/- 4.1) than patients not filmed or those unsure whether they had been filmed (1.6 +/- 2.5); p < 0.01). On a 10-cm VAS where -5 = extreme decrease in satisfaction and 5 = extreme increase in satisfaction, the mean rating by physicians was -0.25 (+/-1.6), by nurses was -0.32 (+/-1.3), and by patients was 0.02 (+/-1.4). There was no statistical difference between the satisfaction levels of providers and patients (p = 0.19). CONCLUSIONS: Providers rated invasion of patient privacy higher than patients rated their own invasion of privacy. Patients who were filmed rated invasion of privacy higher than patients who were not filmed. Filming had no significant effect on the satisfaction of providers or patients.

Adolescent↗
PubMed1991

Urea concentration in minor mucous gland secretions and the effect of salivary film velocity on urea metabolism by Streptococcus vestibularis in an artificial plaque.

Our purpose was to determine the urea concentration in minor mucous gland (MMG) secretions and the pH at proximal and distal aspects of the lower surface of artificial plaque in vitro during infusion of urea solutions over the surface, at different film velocities. Saliva is present in the mouth as a slowly moving film (ca. 0.1 mm thick) with an estimated velocity in the range of 0.8-8.0 mm/min. At low velocities, due to the accumulation of bacterial products, a progressive increase in their concentration may occur in both the plaque and the overlying salivary film at the distal edge (where the film leaves the plaque). S. vestibularis, an oral micro-organism possessing ureolytic activity, was combined with 1% agarose, to give a urease Vmax similar to that of natural plaque. The artificial plaque was in the chamber (6.0 x 6.0 square and 0.5 or 1.5 mm deep) of a diffusion apparatus, and a urea-containing artificial saliva (3.3 or 13.2 mmol/l) was infused over the surface, as a film 0.1 mm deep, at velocities of 0.8, 8.2 and 86.2 mm/min. At the lower (physiologically normal) urea concentration and the two lower film velocities, most urea appeared to be metabolized at the proximal end of the plaque, which developed a higher pH. At the higher urea concentration, and a film velocity of 8 mm/min, a higher pH was found at the distal end. This was probably due to the combination of greater urea availability and a reduced rate of ammonia loss distally. At a film velocity of 86.2 mm/min, proximal/distal pH gradients did not develop.(ABSTRACT TRUNCATED AT 250 WORDS)

Analysis of Variance↗
PubMed1989

Thermal characterization of drug/polymer and excipient/polymer interactions in some film coating formulation.

Some probable consequences of the dissolution/migration of a major solid dosage component in or into an applied film coating during or after a film coating operation have been investigated using free films of hydroxypropyl methylcellulose (HPMC) and polyvinyl alcohol (PVA) incorporating small amounts of either lactose (a diluent) or ephedrine hydrochloride (a drug). Intrinsic features of the films such as softening, glass transition, crystallinity and melting were examined by differential scanning calorimetry and thermomechanical analysis. Generally, the results indicate that ephedrine hydrochloride exhibited plasticizing activity in both HPMC and PVA films. On the other hand, incorporation of lactose produced an opposite effect (stiffening) in PVA films as demonstrated by increased glass transition temperature and crystallinity. On the basis of these findings, it was proposed that the undesired presence of a component of a solid dosage core in the applied film coating could significantly alter its end-use properties such as diffusivity and the incidence of film coating defects. It was also shown that the application of the relationship of Moelter & Schweizer (1949) in the evaluation of the plasticizer efficiency of non-homologous additives could pose problems of interpretation.

Chemistry, Pharmaceutical↗
PubMedDate not supplied

Interferometric measurements of dynamic changes of tear film.

Tear film stability plays an important role in the quality of vision. We present an interferometric method for assessing the stability of precorneal tear film in real time. A lateral shearing technique is applied as a noninvasive and sensitive method for investigating tear film stability and the smoothness of the tear film surface by quantitative evaluation of the interference fringe pattern. The evaporation of tears and the appearance of tear film break-up between blinks cause changes in the fringe geometry. For quantitative assessment of the fringe smoothness and consequently of the tear film structure, the fast Fourier transform (FFT) is applied. Four parameters are used to quantitatively estimate dynamic changes in the tear film stability of the cornea 20 s after the eye blink. Examples of examined interferograms recorded in patients with healthy eyes, patients suffering from dry-eye syndrome, and patients wearing contact lenses are given. Significant differences between the stability of the tear film in the healthy eye and that in the dry eye and the eye with a contact lens are observed. The favorable influence of artificial tears applied in patients with dry-eye syndrome or contact lenses is also discussed.

Dry Eye Syndromes↗
PubMedDate not supplied

Heuristic model for understanding x-ray film characteristics.

A simple, heuristic model of a photographic emulsion is described for the purpose of illustrating the fundamental physical processes and emulsion properties which determine the characteristics of an x-ray film (viz., the shape of the H - D curve, film gamma, and film speed). By means of this model, it is shown that the contrast multiplication afforded by an x-ray film (i.e., a film gamma greater than unity) is a direct result of the exponential attenuation of the viewing light by the developed film, and that film gamma is proportional to grain size, grain density, and emulsion thickness. The difference in the H - D curve that is observed when the same film is exposed to light from an intensifying screen or directly to x rays is also predicted by the model.

Models, Theoretical↗
PubMedDate not supplied

Two-film brachytherapy reconstruction algorithm.

We have developed a new isocentric two-film reconstruction algorithm for brachytherapy seed and needle implants. The algorithm has no requirements that the two films be orthogonal, symmetric, or even be taken in a transverse plane. In addition, there is no requirement that the two films even have the same number of images. We have found removal of these usual constraints useful for head and neck implants where images are often obscured by patient anatomy. The inherent image matching ambiguities associated with traditional two-film techniques are minimized by considering the image end points, rather than just the image centroids. For two films, the new algorithm, which considers all image combinations at one time, matches all the end-point images on one film with those on the other, and then reconstructs the end-point positions of the seeds. The algorithm minimizes the difference between the actual images and the projected images from the reconstructed seeds. The new two-film image matching problem is shown to be equivalent to the well-known assignment problem. For an implant of N seeds, this equivalence allows the two-film problem to be solved by an algorithm (ACM algorithm 548) that scales with a polynomial power of N, rather than N! as is usually assumed. An implant of N seeds can be matched and reconstructed in approximately (N/20)2s on a VAX 11/780.

Brachytherapy↗
PubMed1999

Quantitative optical densitometry with scanning-laser film digitizers.

A new process for eliminating two types of artifacts inherent in commercially available transmission scanning-laser film digitizers is presented. The first kind of artifact results in nonreproducible interference-pattern fluctuations as large as 7%. The second kind results in spreading of transmitted light from low-to-high optical density (OD) in regions with rapidly varying ODs, producing errors as large as 50%. These OD artifacts cause the loss of precision for films with low-OD regions (first type) and the loss of accuracy for films with regions of high-OD near high-OD gradients (second type). Test radiochromic films, produced by uniform exposure to a 6 MV photon beam and a high dose rate 192Ir brachytherapy source, along with test radiographic films were used to characterize the artifacts of a commercially available scanning-laser film digitizer. The interference-pattern artifact was eliminated by digitizing the films on a masked diffusing ground-glass scanning bed. The light-transmission artifact was eliminated through discrete-fast-Fourier-transform (DFFT) deconvolution of transmission profiles with measured digitizer line-spread functions. Obtaining precise OD distributions after the DFFT deconvolution required prior removal of the interference-pattern artifact and application of a low-pass Wiener noise filter. Light-transmission artifacts are particularly significant for applications requiring measurement of high-gradient OD distributions, such as brachytherapy or conformal photon-beam film dosimetry and quantitation of two-dimensional electrophoresis gels. Errors as large as 15%-35% occur in OD distributions representative of these applications. The data collection and correction process developed in this study successfully removes these artifacts.

Biophysical Phenomena↗
PubMed2002

Ferroelectric Bi3.25La0.75Ti3O12 films of uniform a-axis orientation on silicon substrates.

The use of bismuth-layered perovskite films for planar-type nonvolatile ferroelectric random-access memories requires films with spontaneous polarization normal to the plane of growth. Epitaxially twinned a axis-oriented La-substituted Bi4Ti3O12 (BLT) thin films whose spontaneous polarization is entirely along the film normal were grown by pulsed laser deposition on yttria-stabilized zirconia-buffered Si(100) substrates using SrRuO3 as bottom electrodes. Even though the (118) orientation competes with the (100) orientation, epitaxial films with almost pure (100) orientation were grown using very thin, strained SrRuO3 electrode layers and kinetic growth conditions, including high growth rates and high oxygen background pressures to facilitate oxygen incorporation into the growing film. Films with the a-axis orientation and having their polarization entirely along the direction normal to the film plane can achieve a remanent polarization of 32 microcoulombs per square centimeter.

Journal Article↗
PubMed1994

Methods for assessment of biodegradability of plastic films in soil.

Traditional and novel techniques were tested and compared for their usefulness in evaluating biodegrad-ability claims made for newly formulated "degradable" plastic film products. Photosensitized polyethylene (PE), starch-PE, extensively plasticized polyvinyl chloride (PVC), and polypropylene (PP) films were incorporated into aerobic soil. Biodegradation was measured for 3 months under generally favorable conditions. Carbon dioxide evolution, residual weight recovery, and loss of tensile strength measurements were supplemented, for some films, by gas chromatographic measurements of plasticizer loss and gel permeation chromatographic (GPC) measurement of polymer molecular size distribution. Six- and 12-week sunlight exposures of photosensitized PE films resulted in extensive photochemical damage that failed to promote subsequent mineralization in soil. An 8% starch-PE film and the plasticized PVC film evolved significant amounts of CO(2) in biodegradation tests and lost residual weight and tensile strength, but GPC measurements demonstrated that all these changes were confined to the additives and the PE and PVC polymers were not degraded. Carbon dioxide evolution was found to be a useful screening tool for plastic film biodegradation, but for films with additives, polymer biodegradation needs to be confirmed by GPC. Photochemical cross-linking of polymer strands reduces solubility and may interfere with GPC measurements of polymer degradation.

Journal Article↗
PubMed2001

Effect of seeing tobacco use in films on trying smoking among adolescents: cross sectional study.

OBJECTIVE: To test the hypothesis that greater exposure to smoking in films is associated with trying smoking among adolescents. DESIGN: Cross sectional survey of 4919 schoolchildren aged 9-15 years, and assessment of occurrence of smoking in 601 films. SETTING: Randomly selected middle schools in Vermont and New Hampshire, USA. MAIN OUTCOME MEASURE: Number of schoolchildren who had ever tried smoking a cigarette. RESULTS: The films contained a median of 5 (interquartile range 1-12) occurrences of smoking. The typical adolescent had seen 17 of 50 films listed. Exposure to smoking in films varied widely: median 91 (49-152) occurrences. The prevalence of ever trying smoking increased with higher categories of exposure: 4.9% among students who saw 0-50 occurrences of smoking, 13.7% for 51-100 occurrences, 22.1% for 101-150, and 31.3% for >150. The association remained significant after adjustment for age; sex; school performance; school; parents' education; smoking by friend, sibling, or parent; and receptivity to tobacco promotions. The adjusted odds ratios of ever trying smoking for students in the higher categories of exposure, compared with students exposed to 0-50 occurrences of smoking in films, were 1.7 (95% confidence interval 1.2 to 2.4), 2.4 (1.7 to 3.4), and 2.7 (2.0 to 3.8). These odds ratios were not substantially affected by adjustment for parenting style or for personality traits of the adolescent. CONCLUSION: In this sample of adolescents there was a strong, direct, and independent association between seeing tobacco use in films and trying cigarettes, a finding that supports the hypothesis that smoking in films has a role in the initiation of smoking in adolescents.

Adolescent↗