Langmuir and Langmuir-Blodgett films of poly[2-methoxy-5-(n-hexyloxy)-p-phenylenevinylene]

Langmuir films have been fabricated from poly[(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene] (OC1OC6-PPV). The stability and the area per monomer for condensed films indicate the formation of true monolayers with a very small extent of aggregation, which is unusual for polymer films. This is attributed to the linearity of the alkyl side chain. The Y-type Langmuir-Blodgett (LB) films produced from Langmuir films of OC1OC6-PPV have distinctive features compared to those of cast films, probably due to the organization in the LB films whereas the molecules are randomly oriented in cast films. Infrared absorption spectra recorded for both transmission and reflection modes indicate that OC1OC6-PPV molecules are anchored to the substrate by the lateral groups. This is confirmed by the Raman spectrum, in which a distortion of the vinylene group was observed, and by surface enhanced fluorescence (SEF) on an LB monolayer deposited onto Ag nanoparticles. The more homogeneous nature of the LB films in comparison with the case of cast films was demonstrated by optical microscopy and fluorescence measurements where the emission spectra were essentially the same for different regions of an LB film but showed dispersion in cast films. The LB films also displayed reversible photoconductivity.

Incorporation of a liquid crystal to enhance the luminescence properties of Langmuir-Blodgett films of OC1OC6-PPV

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

RELATIONSHIPS BETWEEN THE PLASMA ENVIRONMENT AND THE COMPOSITION AND OPTICAL-PROPERTIES OF PLASMA-POLYMERIZED THIN-FILMS PRODUCED IN RF DISCHARGES OF C2H2-SF6 MIXTURES

Polymer films were grown in rf discharges containing different proportions of C2H2 and SF6. Quantitative optical emission spectrometry (actinometry) was used to follow the trends in the plasma concentrations of the species H and F, and more tentatively, of CH, CF, and CF2, as a function of the feed composition. Infrared spectroscopy revealed the density of CH and CF bonds in the deposited material. As the partial pressure of SF6 in the feed was increased, the degree of fluorination of the polymer also rose. The form of the dependency of the deposition rate on the proportion of SF6 in the feed was in good qualitative agreement with the activated growth model. From transmission ultraviolet visible spectroscopy data the refractive index and the absorption coefficient of the polymers were calculated as a function of the deposition parameters. Since the optical gap depended to some extent upon the degree of fluorination, it could, within limits, be determined by a suitable choice of the proportion of SF6 in the feed. A qualitative explanation of this relationship is given.

The improvement of thin polymer film properties through plasma immersion ion implantation and deposition technique

Thin polymer films were deposited from acetylene and argon mixtures by plasma immersion ion implantation and deposition. The effect of the pulse frequency, v, on molecular structure, optical gap, contact angle and hardness of the films was investigated. It was observed progressive dehydrogenation of the samples and increment in the concentration of unsaturated carbon bonds as the pulse frequency was increased. Film hardness and contact angle increased and optical gap decreased with v. These results are interpreted in terms of the chain unsaturation and crosslinking.

Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Crystallization and optical properties of CCTO thin films under pressure influence

CCTO thin films were deposited on Pt(111)/Ti/SiO 2/Si substrates using a chemical (polymeric precursor) and pressure method. The pressure effects on the CCTO thin films were evaluated by XRD, FEG-SEM and optical properties. Pressure films were found to be more homogeneous and dense than chemical deposition films. Pressure also leaded to an increase in the photoluminescence emission; it is suggested that the displacement of Ti in the titanate clusters, favors the charge transference from TiO 6 to [TiO 5V o z], TiO 5V o z] to [CaO 11V o z] and [TiO 5V o z] to [CuO 4] x. The low synthesis temperature used in the pressure method allows the deposition of films on less expensive substrates (i.e. glass, aluminum, polymer and others).

Running holograms in azopolymer films

We report investigations on running holograms recorded in an azopolymer film made of a poly(methyl methacrylate) matrix doped with Disperse Red 1. Two-wave mixing experiments were carried out in the symmetrical transmission geometry. A stabilization technique was employed for active control of the phase shift between the real-time hologram and the interference pattern. Depending on the imposed phase shift, a running hologram propagates in the material in the form of an isomerization wave created by a continuous erasing-rewriting process. Diffraction efficiencies and the hologram velocities were measured as functions of the holographic phase shift at the wavelengths 515 and 488 nm. The experimental results were compared to theoretical curves obtained from a simplified model of the isomerization kinetics. The selective contributions of the phase and the amplitude gratings to the whole hologram were also determined. © 2013 Springer-Verlag Berlin Heidelberg.

Films from resistant starch-pectin dispersions intended for colonic drug delivery

Free films were obtained by the solvent casting method from retrograded starch-pectin dispersions at different polymer proportions and concentrations with and without plasticizer. Film forming dispersions were characterized according to their hardness, birefringence and rheological properties. The polymer dispersions showed a predominantly viscous behavior (G″ > G′) and the absence of plasticizers lead to building of stronger structures, while the occurrence of Maltese crosses in the retrograded dispersions indicates the occurrence of a crystalline organization. Analyses of the films included mechanical properties, thickness, superficial and cross sectional morphology, water vapor permeability, liquid uptake ability, X-ray diffractometry, in vitro dissolution and enzymatic digestion. The high resistant starch content (65.8-96.8%) assured the resistance of materials against enzymatic digestion by pancreatin. Changes in the X-ray diffraction patterns indicated a more organized and crystalline structure of free films in relation to isolated polymers. Increasing of pectin proportion and pH values favored the dissolution and liquid uptake of films. Films prepared with lower polymer concentration presented better barrier function (WVP and mechanical properties). © 2013 Elsevier Ltd. All rights reserved.

Acetylene plasma polymer treated by atmospheric dielectric barrier discharge

Plasma polymer films are very attractive for industrial applications in several sectors such as in the electronic, mechanic, biomedic, coating and others, due to its good adhesion, being insoluble in mild acids and bases and having a high crosslinking structure. This work reports the physical, structural, and surface properties of the polymer obtained from an acetylene plasma polymerization technique and treated by dielectric barrier discharge (DBD). The film was deposited in a reactor supplied by a radio-frequency power source at low pressure. After deposition, the nanofilms were treated in a DBD plasma reactor operating in air. The treatment times varied from 1 to 5 min. The analysis of molecular structure of the samples was investigated by FTIR spectroscopy, showing absorption bands in 3480, 2930, 1720, 1450 and 1380 cm(-1). The water contact-angle was investigated by goniometric technique and presented values from 5 to 65 degrees. The aging effect of these films was also studied. The alteration in the films surface morphology was assessed by an atomic force microscopy (AFM) which indicated that the roughness increased from 60 nm to 160 nm as a result of the DBD treatment. The refractive index of the samples presented values near 1.7, measured by UV-Visible spectroscopy. (C) 2014 Elsevier Ltd. All rights reserved.

Influence of Mg on the structural and optical properties of LiNbO3 thin films grown by polymeric precursor method

A polymeric precursor solution was used to deposit pure and Mg doped LiNbO3 thin films on sapphire substrates by spin-coating. The effects of magnesium addition on crystallinity, morphology and optical properties of the annealed films were investigated. X-ray diffraction patterns indicate the oriented growth of the films. Phi-scan diffraction evidenced the epitaxial growth with two in-plane variants. AFM studies show that the films are very homogeneous, dense and present smooth surfaces. The refractive index and optical losses obtained by the prism coupling method were influenced by the magnesium addition.

Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.

Polymer surfaces on small length- and short time-scales

The behaviour of a polymer depends strongly on the length- and time scale as well as on the temperature rnat which it is probed. In this work, I describe investigations of polymer surfaces using scanning probe rnmicroscopy with heatable probes. With these probes, surfaces can be heated within seconds down to rnmicroseconds. I introduce experiments for the local and fast determination of glass transition and melting rntemperatures. I developed a method which allows the determination of glass transition and melting rntemperatures on films with thicknesses below 100 nm: A background measurement on the substrate was rnperformed. The resulting curve was subtracted from the measurement on the polymer film. The rndifferential measurement on polystyrene films with thicknesses between 35 nm and 160 nm showed rncharacteristic signals at 95 ± 1 °C, in accordance with the glass transition of polystyrene. Pressing heated rnprobes into polymer films causes plastic deformation. Nanometer sized deformations are currently rninvestigated in novel concepts for high density data storage. A suitable medium for such a storage system rnhas to be easily indentable on one hand, but on the other hand it also has to be very stable towards rnsurface induced wear. For developing such a medium I investigated a new approach: A comparably soft rnmaterial, namely polystyrene, was protected with a thin but very hard layer made of plasma polymerized rnnorbornene. The resulting bilayered media were tested for surface stability and deformability. I showed rnthat the bilayered material combines the deformability of polystyrene with the surface stability of the rnplasma polymer, and that the material therefore is a very good storage medium. In addition we rninvestigated the glass transition temperature of polystyrene at timescales of 10 µs and found it to be rnapprox. 220 °C. The increase of this characteristic temperature of the polymer results from the short time rnat which the polymer was probed and reflects the well-known time-temperature superposition principle. rnHeatable probes were also used for the characterization of silverazide filled nanocapsules. The use of rnheatable probes allowed determining the decomposition temperature of the capsules from few rnnanograms of material. The measured decomposition temperatures ranged from 180 °C to 225 °C, in rnaccordance with literature values. The investigation of small amounts of sample was necessary due to the rnlimited availability of the material. Furthermore, investigating larger amounts of the capsules using rnconventional thermal gravimetric analysis could lead to contamination or even damage of the instrument. rnBesides the analysis of material parameters I used the heatable probes for the local thermal rndecomposition of pentacene precursor material in order to form nanoscale conductive structures. Here, rnthe thickness of the precursor layer was important for complete thermal decomposition. rnAnother aspect of my work was the investigation of redox active polymers - Poly-10-(4-vinylbenzyl)-10H-rnphenothiazine (PVBPT)- for data storage. Data is stored by changing the local conductivity of the material rnby applying a voltage between tip and surface. The generated structures were stable for more than 16 h. It rnwas shown that the presence of water is essential for succesfull patterning.

Development of Optically Based pH Sensing Hydrogel and Controlled Nitric Oxide Release Polymer

Nitric oxide has the potential to greatly improve intravascular measurements by locally inhibiting thrombus formation and dilating blood vessels. pH, the partial pressure of oxygen, and the partial pressure of carbon dioxide are three arterial blood parameters that are of interest to clinicians in the intensive care unit that can benefit from an intravascular sensor. This work explores fabrication of absorbance and fluorescence based pH sensing chemistry, the sensing chemistries' compatibility with nitric oxide, and a controllable nitric oxide releasing polymer. The pH sensing chemistries utilized various substrates, dyes, and methods of immobilization. Absorbance sensing chemistries used sol-gels, fumed silica particles, mesoporous silicon oxide, bromocresol purple, phenol red, bromocresol green, physical entrapment, molecular interactions, and covalent linking. Covalently linking the dyes to fumed silica particles and mesoporous silicon oxide eliminated leaching in the absorbance sensing chemistries. The structures of the absorbance dyes investigated were similar and bromocresol green in a sol-gel was tested for compatibility with nitric oxide. Nitric oxide did not interfere with the use of bromocresol green in a pH sensor. Investigated fluorescence sensing chemistries utilized silica optical fibers, poly(allylamine) hydrogel, SNARF-1, molecular interactions, and covalent linking. SNARF-1 covalently linked to a modified poly(allylamine) hydrogel was tested in the presence of nitric oxide and showed no interference from the nitric oxide. Nitric oxide release was controlled through the modulation of a light source that cleaved the bond between the nitric oxide and a sulfur atom in the donor. The nitric oxide donor in this work is S-nitroso-N-acetyl-D-penicillamine which was covalently linked to a silicone rubber made from polydimethylsiloxane. It is shown that the surface flux of nitric oxide released from the polymer films can be increased and decreased by increasing and decreasing the output power of the LED light source. In summary, an optical pH sensing chemistry was developed that eliminated the chronic problem of leaching of the indicator dye and showed no reactivity to nitric oxide released, thereby facilitating the development of a functional, reliable intravascular sensor.

Micro- and nanostructured polymer substrates for biomedical applications

Polymer implants are interesting alternatives to the contemporary load-bearing implants made from metals. Polyetheretherketone (PEEK), a well-established biomaterial for example, is not only iso-elastic to bone but also permits investigating the surrounding soft tissues using magnetic resonance imaging or computed tomography, which is particularly important for cancer patients. The commercially available PEEK bone implants, however, require costly coatings, which restricts their usage. As an alternative to coatings, plasma activation can be applied. The present paper shows the plasma-induced preparation of nanostructures on polymer films and on injection-molded micro-cantilever arrays and the associated chemical modifications of the surface. In vitro cell experiments indicate the suitability of the activation process. In addition, we show that microstructures such as micro-grooves 1 μm deep and 20 μm wide cause cell alignment. The combination of micro-injection molding, simultaneous microstructuring using inserts/bioreplica and plasma treatments permits the preparation of polymer implants with nature-analogue, anisotropic micro- and nanostructures.