Modification of a Polymer Surface by Partial Swelling Using Nonsolvents

Scanning tunneling microscopy (STM) has been used to characterize the surface roughness of nonlinear optical (NLO) polymers. A review of STM of polymer surfaces is included in this volume. The NLO polymers are instrumental in the development of electrooptical waveguide devices, the most fundamental of which is the modulator. The most common modulator design is the Mach Zehnder interferometer, in which the input light is split into two legs and then recombined into a common output within the two dimensional waveguide. A π phase retardation, resulting in total light extinction at the output of the interferometer, can be achieved by changing the refractive index of one leg with respect to the other using the electrooptic effect. For best device performance, it is essential that the NLO polymer exhibit minimal surface roughness in order to reduce light scattering. Scanning tunneling microscopy, with its high lateral and vertical resolution, is capable of quantifying the NLO polymer surface roughness induced by processing. Results are presented below in which STM was used to measure the surface roughness of films produced by spin-coating NLO-active polymers onto silicon substrates.

Excimer laser irradiation has been used to interferometrically ablate submicron line patterns on to Kapton polyimide. Such patterned material may exhibit highly anisotropic conduction as was predicted from previous studies showing enhanced conductivity from uniformly ablated material. We are currently exploiting this phenomenon to create integrated devices using conventional polymers as both dielectrics and conductors. Extensive scanning electron microscopy (SEM) and limited transmission electron microscopy (TEM) have been conducted in order to characterize the morphology of such patterned nanostructures as a function of processing conditions.The ablation technique employed produces an interference pattern on the polymer surface of period equal to half that of a diffraction grating period, independent of the laser wavelength. In these experiments, a 328 nm grating has been used to produce line patterns of 164 nm line-spacings as shown in Figures 1 and 2. A 200 Å Au coating has been used to both prevent charging and, perhaps more importantly, enhance contrast.

It has been shown that there are numerous advantages in imaging both coated and uncoated polymers in scanning electron microscopy (SEM) at low voltages (LV) from 0.5 to 2.0 keV compared to imaging at conventional voltages of 10 to 20 keV. The disadvantages of LVSEM of degraded resolution and decreased beam current have been overcome with the new generation of field emission gun SEMs. In imaging metal coated polymers in LVSEM beam damage is reduced, contrast is improved, and charging from irregularly shaped features (which may be unevenly coated) is reduced or eliminated. Imaging uncoated polymers in LVSEM allows direct observation of the surface with little or no charging and with no alterations of surface features from the metal coating process required for higher voltage imaging. This is particularly important for high resolution (HR) studies of polymers where it is desired to image features 1 to 10 nm in size. Metal sputter coating techniques produce a 10 - 20 nm film that has its own texture which can obscure topographical features of the original polymer surface. In examining thin, uncoated insulating samples on a conducting substrate at low voltages the effect of sample-beam interactions on image formation and resolution will differ significantly from the effect at higher accelerating voltages. We discuss here sample-beam interactions in single crystals on conducting substrates at low voltages and also present the first results on HRSEM of single crystal morphologies which show some of these effects.

SummaryTissue plasminogen activator labeled with radioactive iodine (125I-tPA) was immobilized on vascular prostheses chemically modified with a thin coating of water-insoluble surfactant, tridodecylmethylammonium chloride (TDM AC). Surfactant- treated Dacron, polytetrafluoroethylene (PTFE), silastic, polyethylene and polyurethane bound appreciable amounts of 125I- tPA (5-30 μg 125I-tPA/cm2). Upon exposure to human plasma, the amount of 125I-tPA bound to the surface shows an initial drop during the first hour of incubation, followed by a slower, roughly exponential release with a t½ of appoximately 75 hours. Prostheses containing bound tPA show fibrinolytic activity as measured both by lysis of clots formed in vitro, and by hydrolysis of a synthetic polypeptide substrate. Prior to incubation in plasma, tPA bound to a polymer surface has an enzymic activity similar, if not identical to that of the native enzyme in buffered solution. However, exposure to plasma causes a decrease in the fibrinolytic activity of both bound tPA and enzyme released from the surface of the polymer. These data demonstrate that surfactant-treated prostheses can bind tPA, and that these chemically modified devices can act as a slow-release drug delivery system with the potential for reducing prosthesis-induced thromboembolism.

<p>Nanostructured wrinkles were developed on fully bio-based poly(trimethylene furanoate) (PTF) films by using the technique of Laser Induced Periodic Surface Structures (LIPSS). We investigated the effect of irradiation time on wrinkle formation using an UV pulsed laser source, at a fluence of 8 mJ/cm2. It was found that the pulse range between 600 and 4800 pulses allowed formation of periodic nanometric ripples. The nanostructured surface was studied using a combined macro- and nanoscale approach. We evaluated possible physicochemical changes taking place on the polymer surface after irradiation by infrared spectroscopy, contact angle measurements and atomic force microscopy. The macroscopic physicochemical properties of PTF showed almost no changes after nanostructure formation, differently from the results previously found for the terephthalic counterparts, as poly(ethyleneterephthalate), PET, and poly(trimethyleneterephthalate), PTT. The surface mechanical properties of the nanostructured PTF were found to be improved, as evidenced by nanomechanical force spectroscopy measurements. In particular, an increased Young’s modulus and higher stiffness for the nanostructured sample were measured. <br></p>

Atomic force microscopy-infrared microscopy (AFM-IR) provides a route to bypass Abbe’s diffraction limit through photothermal detections of infrared absorption. With the combination of total internal reflection, AFM-IR can operate in the aqueous phase. However, AFM-IR in contact mode suffers from surface damage from the lateral shear force between the tip and sample, and can only achieve 20~25-nm spatial resolution. Here, we develop the liquid-phase peak force infrared (LiPFIR) microscopy that avoids the detrimental shear force and delivers an 8-nm spatial resolution. The non-destructiveness of the LiPFIR microscopy enables <i>in situ</i> chemical measurement of heterogeneous materials and investigations on a range of chemical and physical transformations, including polymer surface reorganization, hydrogen-deuterium isotope exchange, and ethanol-induced denaturation of proteins. We also perform LiPFIR imaging of the budding site of yeast cell wall in the fluid as a demonstration of biological applications. LiPFIR unleashes the potential of in liquid AFM-IR for chemical nanoscopy.