Film Chemistry Control Research Articles

Surface functionalization of an osteoconductive filler by plasma polymerization of poly(ε-caprolactone) and poly(acrylic acid) films

One of the major limitations found in the use of nanocomposites based on synthetic hydroxyapatite and polymeric matrix for bone-tissue regeneration lies in the poor interfacial adhesion between the inorganic filler and the polymer matrix. The integrity of the nanocomposite is severely compromised since, on the one hand, high surface fillers tend to form aggregates and on the other, there is no chemical bonding between these two different categories of materials. Thus, customized surface functionalization stands as an effective route to improve the interfacial behaviour between particles and polymeric matrices. Amongst the current state of development of coating technologies, the high film-chemistry controllability offered by plasma polymerization technology enhances the synthesis of polymeric films from virtually any starting organic monomer. In this sense, the work presented here provides strong evidences of surface functionalization achieved by plasma polymerization starting respectively from ε-caprolactone and acrylic acid monomers. The chemistry of the deposited films has been descriptively analysed by XPS demonstrating outstanding retention of monomer functionalities and FTIR spectra of the deposited films revealed a high resemblance to those obtained by conventional synthesis. Results provided thereof are expected to significantly contribute to improve the interfacial behaviour in terms of matrix-reinforcement compatibilization, of crucial importance for bone-tissue engineering applications.

Film Chemistry Control and Growth Kinetics of Pulsed Plasma-Polymerized Aniline

The polymerization of aniline under continuous and pulsed RF-plasma conditions is studied using the same plasma reactor. The effects of input power, on and off-times, frequency and duty cycle variations on the growth kinetics and on the chemical structure of the obtained layers are examined. The chemical structure of the films is characterized using Fourier Transform Infra-Red, X-ray photoelectron and UltraViolet–Visible spectroscopies. The thickness of the films is determined by profilometry. The results show a strong dependence of film chemistry and deposition rates on the discharge power and on-time. The film deposited by pulsed plasma grows mainly during the plasma-on period. Furthermore, this work shows that the retention of aromatic rings can be evaluated by Fourier transform infrared analysis whereas oxidation degree of plasma polyaniline can be determined by X-ray photoelectron and UV–Vis spectroscopies.

Molecular Tailoring of Surfaces via Pulsed Plasma Polymerization.

The use of a variable duty cycle pulsed plasma, in lieu of the conventional continuous-wave operational mode, is employed to provide enhanced film chemistry control during polymer film formation. This film chemistry control is illustrated with studies of perfluorocarbon polymers and by synthesis of electrically conductive films from pyrrole. The ability to synthesize polymer films under very low power inputs, using the pulsed technique, permits generation of relatively linear polymeric structures. Contrasts in several important plasma variables under continuous and pulsed modes are identified and discussed in terms of their influence in providing added film chemistry control under pulsed conditions

Pulsed-plasma polymerization of 1-vinyl-2-pyrrolidone: Synthesis of a linear polymer

The RF plasma induced polymerization of 1-vinyl-2-pyrrolidone was examined under variable duty-cycle pulsed-plasma conditions. Large-scale progressive changes in the composition of the resultant polymeric films were observed with sequential changes in the plasma duty cycle employed during polymerization, all other plasma variables held constant. The film compositional changes obtained are in the direction of increased retention of the lactam ring of the monomer in the resultant polymers as the duty cycles employed (i.e., the ratio of plasma on to plasma off times) were decreased. Particularly significant are the relatively linear polymeric structures obtained under the exceptionally low-average power deposition conditions made accessible with the pulsed plasma technique. XPS and FTIR spectroscopic examination of these latter films reveal compositions that are similar to those obtained by conventional (i.e., nonplasma) synthesis of the linear polymer. The film chemistry controllability demonstrated in the present study is achieved while maintaining the many advantages of the plasma polymerization approach for surface modifications. This work provides additional support for use of the pulsed operational mode as an effective means of film chemistry control, in particular extending the plasma polymerization technique to include synthesis of linear polymers, in lieu of the more highly crosslinked structures typically produced in conventional continuous-wave plasma polymerization processes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3121–3129, 1998

Surface Molecular Tailoring via Pulsed Plasma-Generated Acryloyl Chloride Polymers: Synthesis and Reactivity

A variable-duty cycle-pulsed radio frequency discharge is shown to provide film chemistry control during plasma polymerization of acryloyl chloride. A nonlinear dependence is observed between the percent retention of acid chloride groups in the deposited films and the average power input during plasma polymerization. Significant C(O)Cl group retention is observed only under conditions of exceptionally low power input, as made available in the pulsed experiments. Additionally, relatively large scale systematic changes in surface morphology and film formation rates are observed with sequential variations in the plasma duty cycle employed during film formation. Specifically, film surface roughness decreases and the film thickness per joule of input energy increases as the plasma duty cycles employed are decreased. The plasma-generated films were employed in subsequent chemical reactions to attach target molecules to the substrate surfaces via facile reactions with the surface acid chloride groups. This conce...

Pulsed Plasma Polymerizations: Film Chemistry Control and Applications

AbstractFilm chemistry control issues, as well as key properties of polymers synthesized under pulsed plasma conditions, are discussed. Distinctions between pulsed and continuous wave plasmas are examined, particularly as they relate to differences in the energy efficiency of film formation rates and to the range of available power inputs. Film stabilities, with special reference to polymers formed under very low power input conditions, are considered. Finally, selected applications involving use of the inherently high film chemistry controllability made available by the variable duty cycle pulsed plasma technique are described.

Reduced protein adsorption on plastics via direct plasma deposition of triethylene glycol monoallyl ether.

The direct plasma-induced deposition of tri(ethylene glycol) monoallyl ether is reported. RF plasma polymerization of this monomer was carried out under both continuous wave (CW) and pulsed plasma operation. The major focus of this work was optimization of the degree of retention of the C-O-C bonds of the starting monomer during the deposition process. This successfully was accomplished using low RF power during the CW runs and low RF duty cycles during the pulsed plasma experiments. Spectroscopic analysis of the plasma films revealed a strong dependence of film composition on the RF power and duty cycles employed. In particular, an unusually high level of film chemistry compositional control was demonstrated for the pulsed plasma studies, with film composition varying in a steady, progressive fashion with sequential changes in the ratios of plasma on to plasma off times. This film chemistry controllability is demonstrated despite the relatively low volatility of the starting monomer. The utility of this plasma deposition approach in introducing polyethylene oxide (PEO) structures on solid substrates was evaluated via protein adsorption studies. Radiolabeled bovine albumin adsorption was studied on plasma-modified poly(ethylene teraphthalate) (PET) substrates. Dramatic reductions in both initial adsorption and retention of this protein were observed on PET samples having maximal PEO content relative to its adsorption on untreated PET surfaces. Good stability and adhesion of the plasma films to the underlying PET substrates were observed, as evidenced from prolonged immersion of plasma-treated surfaces in aqueous solution. Overall, the results obtained from the present work provide additional support for the utility of one-step plasma process to reduce biological fouling of surfaces via deposition of PEO surface units.

Molecular Tailoring of Surfaces: Pulsed Plasma Polymerization of Bromine Containing Monomers

The use of a variable duty cycle pulsed RF plasma is shown to provide film chemistry control during polymerization of saturated (CH2Br2) and unsaturated (CH2=CHCH2Br) bromine containing monomers. With both monomers, the degree of bromine atom retention in the films is observed to increase in a progressive fashion as the RF duty cycle employed during plasma polymerization is decreased. The film deposition rates, when expressed in terms of thickness per Joule of RF energy input, increase rapidly as the RF duty cycles are reduced. Additionally, the film morphology is observed to become increasingly smooth with decreasing RF duty cycles during deposition, as illustrated with the allyl bromide monomer. The film chemistry controllability of this study is demonstrated with monomers possessing the relatively weak C-Br bond. As such, the present work represents an important extension of the pulsed plasma polymerization approach to include retention of a labile bond during film formation. The introduction of reactive surface functional groups, at controlled densities, provides additional molecular tailoring possibilities via subsequent chemical derivatization processes.

Pulsed Radio Frequency Plasma Polymerization of Allyl Alcohol: Controlled Deposition of Surface Hydroxyl Groups

The utility of employing a variable duty cycle pulsed plasma polymerization technique to control film chemistry during plasma depositions is examined using allyl alcohol as monomer gas. Large scale progressive variations in film composition are observed with sequential changes in the plasma duty cycles employed, all other plasma variables being held constant. In particular, the −OH functionality of the monomer is increasingly retained in the plasma generated thin films as the radio frequency duty cycle is lowered. Fourier transform infrared and X-ray photoelectron spectroscopic analyses of the films obtained reveal that excellent film chemistry control is achieved during plasma polymerization of this monomer. The surface density controllability of functional groups, coupled with a gradient layering technique described herein to improve film adhesion to substrate surfaces, provides ideal opportunities for molecular tailoring of surfaces via subsequent derivatization reactions.