Systematic variation in the electrical conductivity of poly(3,4-ethylenedioxythiophene) (PEDOT) was achieved by oxidative chemical vapor deposition (oCVD). For oCVD, both the oxidant, Fe(III)Cl3, and ...3,4-ethylenedioxythiophene (EDOT) monomer are introduced in the vapor phase. A heated crucible allows for sublimation of the oxidant directly into the reactor chamber operating at 150 mTorr. Spontaneous reaction of the oxidant with the monomer introduced though a feedback-controlled mass flow system results in the rapid (>200 nm thick film in 30 min) formation of π-conjugated PEDOT thin films directly onto a temperature-controlled substrate. As the substrate temperature is increased from 15 to 110 °C, increasing conjugation length, doping level, and electrical conductivity of the PEDOT chains are observed by UV−vis absorption spectroscopy (UV−vis), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. Concomitantly, the measured electrical conductivity of the PEDOT films increases systematically with an apparent activation energy of 28.2 ± 1.1 kcal/mol.
Copolymer films of poly(4-vinylpyridine-co-ethylene glycol diacrylate) (p(4-VP-co-EGDA)) were synthesized and first deposited on various substrates via initiated chemical vapor deposition (iCVD). ...As-deposited copolymer films were converted to surface zwitterionic structures containing poly(carboxybetaine acrylic acetate) (pCBAA) units by a quaternization reaction with 3-bromopropionic acid (3-BPA). Conversion to a zwitterionic structure was confirmed by FTIR and high-resolution XPS N1s scans. Biopolymer adsorption of the deposited copolymer coatings was investigated by quartz crystal microbalance with dissipation (QCM-D) using a model foulant‐bovin serum albumin (BSA). The optimized copolymer films were then deposited onto commercial RO membranes and with subsequent zwitterionicalization. Inertness to bacterial adhesion of the modified membranes was investigated by counting the number of Escherichia coli and Pseudomonas aeruginosa cells attached on the membrane surface under static conditions. Bacterial adhesion studies revealed an almost 98% reduction in micro-organism attachment onto the surface of modified membranes compared to bare membranes, which clearly demonstrates the effectiveness and superior performance of the zwitterionic coating against bacterial adhesion. The salt rejection performance of the modified membranes resulted in improved salt rejection (98%); however, permeate flux was slightly compromised compared to virgin membranes. AFM analysis demonstrated that modified membranes showed lower RMS roughness compared to virgin membranes.
•Surface modification of commercial RO desalination membranes•p(4VP-co-EGDA) co-polymerization via initiated chemical vapor deposition•Functionalization of the co-polymer to carboxybetaine zwitterion surface moieties•Significant reduction of bacterial cell attachment on modified membrane surface•Perm selectivity under cross flow conditions comparable to virgin membranes
Polymeric membranes have been applied in industrial gas separations for decades. Competing technologies, such as cryogenic distillation and sorption processes, require the gases to be either ...condensed or thermally regenerated from the sorbents. In contrast, membrane gas separation does not involve phase transition, representing the potential for a more energy efficient and eco-friendly separation process. However, the overall energy consumption by membrane gas separation is highly dependent on the quality of the membrane employed for the separation process. With the goal of reducing the energy input needed for creating the transmembrane pressure difference, numerous bulk polymers have been investigated. However, less effort has been devoted to processing polymers into ultrathin membranes and investigating their gas permeation properties, which can be quite different from their bulk counterparts. This review summarizes recent advances in fabricating ultrathin gas-selective polymeric membranes. Several classes of ultrathin polymeric membranes are highlighted: microporous polymers, facilitated transport polymeric membranes, Langmuir-Blodgett (LB) films and Layer-by-Layer (LbL) deposited polyelectrolyte multilayers (PEMs), polyamides and other commercial polymers. The application of gas-selective polymeric membranes beyond gas separation is also included as a meaningful extension to this review.
This review focuses on polymers that can be processed into submicron membranes, their gas separation performances and applications beyond separation.
Polymers with their tunable functionalities offer the ability to rationally design micro- and nano-engineered materials. Their synthesis as thin films have significant advantages due to the reduced ...amounts of materials used, faster processing times and the ability to modify the surface while preserving the structural properties of the bulk. Furthermore, their low cost, ease of fabrication and the ability to be easily integrated into processing lines, make them attractive alternatives to their inorganic thin film counterparts. Chemical vapor deposition (CVD) as a polymer thin-film deposition technique offers a versatile platform for fabrication of a wide range of polymer thin films preserving all the functionalities. Solventless, vapor-phase deposition enable the integration of polymer thin films or nanostructures into micro- and nanodevices for improved performance. In this review, CVD of functional polymer thin films and the polymerization mechanisms are introduced. The properties of the polymer thin films that determine their behavior are discussed and their technological advances and applications are reviewed.
Poly2-(dimethylamino)ethyl methacrylate-co-ethylene glycol dimethacrylate (PDE) thin films were synthesized via initiated chemical vapor deposition (iCVD) and reacted with 1,3-propane sultone to ...obtain the zwitterionic structure. The cross-linker ethylene glycol dimethacrylate (EGDMA) was utilized to make the copolymer insoluble in water. The composition of the copolymer was tuned by varying the flow rates of precursors and calculated from Fourier transform infrared spectroscopy (FTIR) spectra. The zwitterionic coatings were covalently grafted on to reverse osmosis (RO) membranes, and surface characterizations were carried out. Scanning electron microscope (SEM) and atomic force microscope (AFM) revealed that the iCVD zwitterionic coatings were conformal and smooth over the RO membrane, and the coating thickness can be measured by using ellipsometry. Salt rejection was not impaired by the coating. Permeation tests were carried out under different feed pressures, film thicknesses, and film compositions, showing a 15% to 43% reduction in permeation. Cell adhesion tests were carried out using Escherichia coli, and the coated RO membranes showed superior antifouling performance compared with the bare RO membrane. This is the first time that the library of iCVD functional groups has been extended to charged zwitterionic moieties, and the zwitterionic coatings have been applied on delicate substrates, such as RO membranes.
Highoptical transmittance conjugated‐polymers with electrical conductivity are garnering much attention for the applications in organic optoelectronic devices including organic ...field‐effect‐transistors and solar cells. Polymers based on PEDOT are particularly promising candidates with high conductivity, uniform surface planarity and excellent ductility. In this work, homopolymer PEDOT deposited using oxidative chemical‐vapor‐deposition(oCVD) show the maximum conductivity of ≈3500 S/cm. However, their utility is limited due to the relatively low transmittance and abrupt decrease near the red edge in the visible regime. Here, the significantly improved optical properties achieved via tuning the bandgap of cross‐linked PEDOT copolymers using oCVD, offering a single‐step process for the synthesis and deposition of copolymer films, is reported. The cross‐linking monomers of biphenyl or anthracene are simultaneously evaporated with EDOT monomer and an oxidant(FeCl3) during the deposition. Poly(anthracene‐co‐EDOT)p(ANTH‐co‐EDOT) shows the superior transmittance (≈93%) to homopolymer PEDOT (≈80%) and poly(biphenyl‐co‐EDOT)p(BPH‐co‐EDOT) (≈88%). Additionally, copolymers show no transmission decay in the red edge regime unlike homopolymer PEDOT that presents an abrupt transmission falloff. An improvement in optical transmittance is in agreement with an increase in bandgap of materials (p(ANTH‐co‐EDOT), ≈2.3eV vs PEDOT, ≈1.8 eV). oCVD‐processed bandgap‐tunable PEDOT copolymers with enhanced transmittance may, therefore, have applications in organic optoelectronic devices that require high optical transparency.
Band gap‐tuned PEDOT copolymers are successfully demonstrated using oCVD with the incorporation of cross‐linking monomers of anthracene or biphenyl. oCVD offers single‐step synthesis, deposition and doping of copolymers. oCVD copolymers show significantly improved visible‐regime transparency compared to homopolymer PEDOT, which is promising for many organic optoelectronic devices that require high optical transmittance with electrical conductivity.
This review will focus on the controlled release of pharmaceuticals and other organic molecules utilizing polymeric nanolayers grown by initiated chemical vapor deposited (iCVD). The iCVD layers are ...able conform to the geometry of the underlying substrate, facilitating release from one- and two-dimensional nanostructures with high surface area. The reactors for iCVD film growth can be customized for specific substrate geometries and scaled to large overall dimensions. The absence of surface tension in vapor deposition processes allows the synthesis of pinhole-free layers, even for iCVD layers <10 nm thick. Such ultrathin layers also provide rapid transport of the drug across the polymeric layer. The mild conditions of the iCVD process avoid damage to the drug which is being encapsulated. Smart release is enabled by iCVD hydrogels which are responsive to pH, temperature, or light. Biodegradable iCVD layers have also be demonstrated for drug release.
Engineering the texture and nanostructure to improve the electrical conductivity of semicrystalline conjugated polymers must address the rate‐limiting step for charge carrier transport. In highly ...face‐on orientation, the charge transport between chains within a crystallite becomes rate‐limiting, which is highly sensitive to the π–π stacking distance and interchain charge transfer integral. Here, face‐on oriented semicrystalline poly(3,4‐ethylenedioxythiophene) (PEDOT) thin films are grown via water‐assisted (W‐A) oxidative chemical vapor deposition (oCVD). Combining W‐A with the volatile oxidant, antimony pentachloride, yields an optimized electrical conductivity of 7520 ± 240 S cm−1, a record for PEDOT thin films. Systematic control of π–π stacking distance from 3.50 Å down to 3.43 Å yields an electrical conductivity enhancement of ≈1140%. The highest electrical conductivity also corresponds to minimum in Urbach energy of 205 meV, indicating superior morphological order. The figure of merit for transparent conductors, σdc/σop, reaches a maximum value of 94, which is 1.9× and 6.7× higher than oCVD PEDOT grown without W‐A and utilizing vanadium oxytrichloride and iron chloride oxidizing agents, respectively. The W‐A oCVD is single‐step all‐dry process and provides conformal coverage, allowing direct growth on mechanical flexible, rough, and structured surfaces without the need for complex and costly transfer steps.
In poly(3,4‐ethylenedioxythiophene) (PEDOT) thin films with a highly face‐on orientation, the charge transport between chains within a crystallite becomes a rate‐limiting factor, which is highly sensitive to the π–π stacking distance. Engineering the π–π stacking distance in PEDOT films grown by water‐assisted oxidative chemical vapor deposition (oCVD) yields a record high electrical conductivity of 7520 ± 240 S cm−1.
Advanced conductors (such as conducting and semiconducting polymers) are vital building blocks for modern technologies and biocompatible devices as faster computing and smaller device sizes are ...demanded. Conjugated conducting and semiconducting polymers (including poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline (PANI), polythiophene (PTh), and polypyrrole (PPy)) provide the mechanical flexibility required for the next generation of energy and electronic devices. Electrical conductivity, ionic conductivity, and optoelectronic characteristics of advanced conductors are governed by their texture and constituent nanostructures. Thus, precise textural and nanostructural engineering of advanced conjugated conducting and semiconducting polymers provide an outstanding pathway to facilitate their adoption in various technological applications, including but not limited to energy storage and harvesting devices, flexible optoelectronics, bio-functional materials, and wearable electronics. This review article focuses on the basic interconnection among the nanostructure and the characteristics of conjugated conducting and semiconducting polymers. In addition, the application of conjugated conducting and semiconducting polymers in flexible energy devices and the resulting state-of-the-art device performance will be covered.
Fibrous membranes of poly(trimethyl hexamethylene terephthalamide) (PA6(3)T) were fabricated by electrospinning and rendered hydrophobic by applying a conformal coating of ...poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PPFDA) using initiated chemical vapor deposition (iCVD). A set of iCVD-treated electrospun PA6(3)T fiber membranes with fiber diameters ranging from 0.25 to 1.8 μm were tested for desalination using the air gap membrane distillation configuration. Permeate fluxes of 2–11 kg/m2/h were observed for temperature differentials of 20–45 °C between the feed stream and condenser plate, with rejections in excess of 99.98%. The liquid entry pressure was observed to increase dramatically, from 15 to 373 kPa with reduction in fiber diameter. Contrary to expectation, for a given feed temperature the permeate flux was observed to increase for membranes of decreasing fiber diameter. The results for permeate flux and salt rejection show that it is possible to construct membranes for membrane distillation even from intrinsically hydrophilic materials after surface modification by iCVD and that the fiber diameter is shown to play an important role on the membrane distillation performance in terms of permeate flux, salt rejection, and liquid entry pressure.
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