We report photoinitiated chemical vapor deposition (piCVD), a gentle synthetic method for the preparation of ultrathin films (approximately 100 nm) of the hydrogel poly(hydroxyethyl methacrylate) (pHEMA). piCVD occurs near room temperature and requires only mild vacuum conditions. The deposited films swell rapidly and reversibly in buffer solution, and the swelling properties can be controlled via the deposition conditions. Analysis of the swelling data indicates that the mesh size of the hydrogel creates a selectively permeable coating. The mesh is large enough to allow small molecule analytes to permeate the film but small enough to prevent the transport of large biomolecules such as proteins. X-ray photoelectron spectroscopy (XPS) shows that the films decrease nonspecific adhesion of the protein albumin by nearly 8-fold over bare silicon. A dry process, piCVD is suitable for coating particles with diameters as small as 5 microm. The absence of solvents and plasmas in piCVD allows films to be directly synthesized on optode sensors without degradation of sensitivity or response time.

Several property requirements have led to the modification of hydrogels by incorporating functional groups. The current work seeks to achieve graded functional group incorporation into hydrogel thin films using the one-step technique of photoinitiated CVD (piCVD). The functional group pentafluorophenylmethacrylate (PFM) is copolymerized with hydroxyethyl methacrylate (HEMA). Because PFM reacts easily with amine groups, the incorporation of PFM results in a platform for subsequent functionalization. The graded copolymer confines the PFM to the near surface region (∼20 nm) allowing the control of the hydrogel film properties independently of the surface reactivity. Although homogeneous incorporation of PFM in the hydrogel matrix inhibits swelling, the swollen water content of pure pHEMA is nearly preserved in the graded copolymer. FTIR spectroscopy shows that the absorption peaks corresponding to the fluorinated phenyl ring in the graded copolymer disappear after functionalization with O,O-bis (2aminoethyl) polyethylene (PEG-diamine), suggesting a nearly complete conversion of the PFM bonds.

No abstract

Using the iCVD (initiated chemical vapor deposition) polymerization technique, we generated a library of thermosensitive thin film hydrogels in the physiological temperature range. The library shows how a specific hydrogel with a desired temperature response can be synthesized via the copolymerization of three main components: (a) the main thermosensitive monomer, which determines the temperature range of the LCST; (b) the comonomer, which modulates the temperature according to its hydrophilic/hydrophobic behavior; and (c) the cross-linker, which determines the swelling degree and the polymer chain mobility of the resulting hydrogel. The thermosensitive thin films included in the library have been characterized by the water contact angle (WCA), revealing a switchable hydrophobic/hydrophilic behavior depending on the temperature and a decrease in the WCA with the incorporation of hydrophilic moieties. Moreover, a more accurate characterization by quartz crystal microbalance (QCM) is performed. With temperature and flow control, the switchable swelling properties of the thermosensitive thin films (due to the polymer mixture transition) can be recorded and analyzed in order to study the effects of the comonomer moieties on the lower critical solution temperature (LCST). Thus, the LCST tailoring method has been successfully used in this paper, and thermoresponsive thin films (50 nm in thickness) have been deposited by iCVD, exhibiting LCSTs in the 32-49 °C range. Due to the presented method's ability to tailor the LCST in the physiological temperature range, the developed thermoresponsive films present potential biosensing and drug delivery applications in the biomedical field.

No abstract

Diphenyl disulfide is a common agent used in the devulcanization of sulfur-vulcanized goods. Its activity has been tested both in real rubber samples and in model molecules but, to the best of our knowledge, always under normal heating conditions. Moreover, there is a lack of information about how the vulcanizing potential of the molecule can affect the devulcanization yield. In this study, the diphenyl disulfide behavior has been studied in model compound vulcanization, with squalene used as a model molecule of natural rubber. Microwaves have been used as a heating source, and the vulcanization/devulcanization behavior of the molecules has been characterized. The results have shown that it is possible to tailor the diphenyl disulfide activity by controlling the reaction temperature and also through microwave power control.

No abstract

In this paper we present the numerical analysis of the quasi-static behavior of an unbalance cracked shaft with straight and elliptical cracks considering an eccentric mass. The rotation of the shaft has been simulated by considering different angular positions to complete one rotation. The influence of the mass eccentricity in the opening of the crack has been studied considering different angles of eccentricity. The study of the partially opening/closing of the crack in the rotation of the shaft under the influence of the eccentric mass is analyzed. The work allows us to know the influence of the unbalance in the crack breathing mechanism and will help to predict the influence of this behavior on the values of the Stress Intensity Factor and on the propagation of cracks.