Initiated Chemical Vapor Deposition of Poly(1H,1H,2H,2H-perfluorodecyl Acrylate) Thin Films

Abstract

A solvent-free initiated chemical vapor deposition (iCVD) process was used to create low surface energy poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PPFDA) thin films at deposition rates as high as 375 nm/min. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy showed full retention of the fluorine moieties, and no measurable cross-linking was detected. Additionally, the FTIR studies support the hypothesis that film deposition results from vinyl polymerization. For all iCVD PPFDA films, the static contact angle was found to be 120.8 +/- 1.2 degrees. The roughness of the films was found to be between 14.9 and 19.8 nm RMS, and the refractive index of the films was found to be between 1.36 and 1.37. The deposition rate was studied as a function of the substrate temperature and the partial pressure of the monomer. It was found that the deposition rate increases with decreasing substrate temperature and increasing monomer partial pressure. It was also found that the molecular weight increases with decreasing substrate temperature and increases with increasing monomer partial pressure. The highest molecular weight measured was 177 300 with a polydispersity of 2.27. Quartz crystal microbalance (QCM) measurements showed that these effects correlated with an increased monomer concentration at the surface. The deposition rate data and the QCM data were quantitatively analyzed to find the rate constants of the process using a previously published model for the iCVD process involving nonfluorinated monomers. The determined values of the rate constants of the surface polymerization were found to be similar to the rate constants measured in liquid-phase free radical polymerization. The kinetic data found in this paper can now be used to study iCVD deposition onto substrates with more complex geometries.

Polymeric Coatings Deposited From an Aerosol‐Assisted Non‐thermal Plasma Jet

“…The spectra for the monomer liquid and polymeric coatings are largely similar, indicating that the chemistry of the precursor molecule has been largely retained in the coating. [17,18] There was some broadening evident in the CF 2 -and CF 3 -derived peaks in the region of 1100-1250 cm À1 in the plasma-deposited coatings. The broadening is likely to be due to the loss of a number of degrees of freedom as the liquid is transformed into a solid.…”

Linker-free grafting of fluorinated polymeric cross-linked network bilayers for durable reduction of ice adhesion

“…S3, ESI †). [42][43][44] High resolution XPS spectra of F1s and C1s binding energy were also acquired. Atomic percentages of 54.30 and 7.02 were obtained for -CF 2 -and CF 3 groups from the C1s high resolution spectra which indicates that the structure of the monomer unit, including that of the functional pendant group, is completely maintained during iCVD polymerization (Fig.…”

Transparent fluorinate acrylic polyurethane with hydrophobicity obtained by crosslinking of hydroxyl-containing fluoroacrylate copolymer with HDI trimer

“…Fluorinated acrylic polymers, especially with fluoroalkyl side chains are used as components for high performance paint and varnish in the textile, paper, leather, construction, automotive, aerospace industry, optics, and microelectronics [5][6][7][8]. The pendant -CF 3 end groups on the fluoroalkyl side chains would segregate to the surface of polymer films, which would offer the polymer low surface free energy and good water-repellent properties.…”

“…Up to now, many synthesis methods and techniques, such as initiated CVD [5], plasma deposition [18,19], polymerization in SC CO 2 [20], have been developed and used for introducing the pendant -CF 3 end groups into polymers for a waterrepellent surface. Special reaction conditions, expensive equipment and poor adhesion to substrates limit the application of these techniques in coating industry.…”