Effects of the film thickness on the morphology,structure, and crystal orientation behavior of poly(chloro‐p‐xylylene) films

Poly(chloro‐p‐xylylene) (PPXC) films with a thickness range encompassing more than three orders of magnitude (from 10² nm to 10² μm) were prepared on Si substrates by the chemical vapor deposition method under the same conditions. The effect of the film thickness (d) on the morphology, crystal structure, and crystal orientation behavior of the PPXC films was studied. The average roughness of the root mean square (rms) of the films increased with increasing d according to a power law (rms ≈ d^β, where β is an exponent that depends on the film growth process over time and β = 0.240±0.005, as probed by atomic force microscopy), and the monomer diffusion and relaxation of polymer were suggested as the primary factors governing this morphological evolution. The X‐ray diffraction results indicate that both the crystallinity and crystal size of PPXC increased with increasing d due to the surface confinement effect between the film and the substrate, which retarded the crystallization process. The X‐ray pole figures suggested that the (020) fiber textures with the b axis parallel to the Si substrate normal existed in the PPXC films; these fiber textures, mainly composed of edge‐on crystal lamellae, were thermodynamically favored. The Herman's orientation factor of the fiber textures increased gradually as d grew; this indicated that stronger (020) fiber textures with higher concentrations of edge‐on lamellae existed in the thicker PPXC films. This thickness dependence of the crystal orientation behavior was interpreted to be caused by the strong adhesion between the polymer chains and the substrate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41394.     

Interfacial polymerization of polyaniline and its layer‐by‐layer assembly into polyelectrolytes multilayer thin‐films

The layer‐by‐layer (LbL) self assembly deposition technique was used to prepare multilayer thin films of anionic polyaniline‐blend‐poly(sodium 4‐styrenesulfonate) (PANI‐PSS) and cationic poly(diallydimethylammonium chloride) (PDADMAC). Anionic polyaniline was prepared by the interfacial polymerization of aniline monomer in the presence of PSS which acted as template to provide water solubility. The PSS to PANI concentration ratios used in the synthesis step was found to have a major effect on the final PANI‐PSS synthesis, its self assembly and the electrical properties of the prepared films. The optical and electrical properties of the films were measured by ultraviolet‐visible spectroscopy (UV‐Vis) and a 4‐point probe setup, respectively while the thickness of the films was measured by atomic force microscopy (AFM). Results showed that the optimum condition for the film growth and optimal conductivity were obtained with different synthesis conditions. These results suggest that the PSS concentration used for interfacial synthesis of PANI must be finely tuned depending on the type of application aimed by the user. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the radiation grafting conditions on the cross‐sectional distribution of poly(vinylbenzyl chloride) grafted polymer onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

Poly(vinylbenzyl chloride) (PVBC)‐grafted poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films were prepared as precursors for ion‐exchange membranes with a radiation grafting technique. A scanning electron microscopy–energy dispersive X‐ray spectroscopy (SEM‐EDX) instrument was used to investigate the effects of the radiation grafting conditions on the distribution profiles of the grafts in the FEP‐g‐PVBC films because the properties of the ion‐exchange membranes were largely affected not only by the degree of grafting (DOG) but also by the distribution of the graft chain. These results indicate that the distribution profile of the grafts largely depended on the grafting parameters, such as the solvent, monomer concentration, film thickness, and irradiation dose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface grafting polymerization of N‐vinyl‐2‐pyrrolidone onto a poly(ethylene terephthalate) nonwoven by plasma pretreatment and its antibacterial activities

The objective of this research was the surface grafting polymerization of biocompatible monomer N‐vinyl‐2‐pyrrolidone (NVP) onto a plasma‐treated nonwoven poly(ethylene terephthalate) (PET) substrate with ultraviolet (UV)‐induced methods. The effects of various parameters, such as the monomer concentration, reaction time, initiator (ammonium peroxodisulfate) concentration, and crosslinking agent (N,N′‐methylene bisacrylamide) concentration, on the grafting percentage were studied. The grafting efficiency of the modified nonwoven PET surfaces reached a maximum at 50 min of UV irradiation and with a 30 wt % aqueous NVP solution. After the plasma activation and/or grafting, the hydrophobic surface of the nonwoven was modified into a hydrophilic surface. NVP was successfully grafted onto nonwoven PET surfaces. The surface wettability showed that the water absorption of NVP‐grafted nonwoven PET (NVP‐g‐nonwoven PET) increased with increasing grafting time. NVP‐g‐nonwoven PET was verified by Fourier transform infrared spectra and scanning electron microscopy measurements. An antibacterial assessment using an anti‐Staphylococcus aureus test indicated that S. aureus was restrained from growing in NVP‐g‐nonwoven PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 803–809, 2006     

Development of a fast drying hybrid lacquer in a low‐relative‐humidity environment based on kurome lacquer sap

Hybrid lacquers that dry quickly in a low‐relative‐humidity environment were synthesized with the repeated kurome lacquer process and an organic silicone compound. An investigation by gel permeation chromatography showed that fractions with different molecular weights showed a lower monomer concentration than the pure kurome lacquer. Fourier transform infrared spectra of the hybrid lacquers revealed that absorption due to the ether of the quinone olefin and/or dibenzofuran appeared around 1470 and 1080 cm^?1 and increased with the number of drying days. The gel fractions in the lacquer films increased according to the number of drying days, and this showed that the hybrid lacquers had higher gel fractions than the pure kurome lacquer in the initial stage of dryness. In addition, the drying mechanism of the hybrid lacquers was analyzed with an automatic drying time recorder and rigid‐body pendulum physical property testing measurements. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1055–1061, 2005     

Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

Nanometer‐thick patterned conductive films prepared through the self‐synthesis of polythiophene derivatives

The development of flexible electronics requires the patterning of conductive and active semiconductor films. Although inorganic materials such as indium tin oxide and metal nanoparticles have high conductivity and transparency, their poor interfacial adhesion with organic layers, lack of flexibility, high weight and high capital costs are drawbacks. In contrast, organic conducting polymers have great potential for use in commercial flexible electronic applications because of their low production costs, environmental stability and acceptable conductivities. A UV‐curable photoresist containing hydroxyl groups was prepared from a mixture of a photoinitiator, epoxy‐acrylate resin, hydroxyethyl methacrylate and tripropylene glycol diacrylate. Patterns having line widths/spaces of 100/100 µm and 10/5 µm were fabricated on a poly(ethylene terephthalate) (PET) substrate using lithography techniques. (3‐Methyl‐3,4‐dihydro‐2H‐thieno[3,4‐b]dioxepin‐3‐yl)methanol (ProDOT‐OH) was self‐synthesized through urethane linkages onto the surface of the patterned photoresist on the PET film, which was then dipped into a solution of another monomer, 3‐thienylethoxybutanesulfonate (TEBS), and initiator and polymerized in situ to form conductive poly(ProDOT‐OH‐co‐TEBS) films covering the surface of the patterned resist. The optimal conductivity of the poly(ProDOT‐OH‐co‐TEBS) films was ca 90 S cm^?1 with an optical transparency of ca 70%. A new bottom‐up technique has been developed for the preparation of patterned organic transparent conductive films: self‐synthesis of the monomer using urethane‐forming reactions and subsequent in situ polymerization. The conductivity of the films can be controlled by the polymerization reaction time and the resolution of the pattern. These conductive patterned films might be applicable to the manufacture of industrial touch panels or chemical/biological sensors. Copyright © 2009 Society of Chemical Industry     

Protein adsorption materials based on conducting polymers: polypyrrole modified with ω‐(N‐pyrrolyl)‐octylthiol

In order to fabricate a new polymer matrix for application in biochips and to understand the mechanism of adsorption of proteins on conducting polymers, we prepared polypyrrole (PPy) functionalized with ω‐(N‐pyrrolyl)‐octylthiol moieties. The chemical structure of the polymer could be controlled by varying the concentration of pyrrole added as the monomer. Initially, ω‐(N‐pyrrolyl)‐octylthiol was self‐assembled into a monolayer on a gold surface. Thereafter, a layer of uniform and smooth PPy was obtained by the chemical copolymerization of pyrrole and the ω‐(N‐pyrrolyl)‐octylthiol. Bovine serum albumin (BSA) adsorption on the polymer was investigated using surface plasmon resonance spectroscopy and cyclic voltammograms. The chemical structure and monomer components of the as‐prepared films were characterized using Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Water contact angle measurements were used to assess the surface wettability of the films throughout the preparative procedure. The kinetics of BSA adsorption onto the polymer could be controlled by varying the copolymer thickness and the pH value of the buffer solutions used. Moreover, the electroactivity was changed upon BSA binding. The results suggest that the new conducting polymer may potentially be applied as a more sensitive and reliable matrix in protein sensors. Copyright © 2011 Society of Chemical Industry     

Thin film solvent‐free photopolymerization of n‐butyl acrylate. I. Static film studies

The results are presented for a detailed investigation involving the free‐radical photopolymerization of n‐butyl acrylate in the form of thin static films. The aim of this work is to benchmark the performance of a novel thin film spinning disk reactor that may be used for the continuous production of linear polymers using photoinitiation. Industrially relevant film thicknesses (200 μm to 1 mm) are studied as opposed to earlier work that looked into extremely thin films (5–25 μm). Such extreme film thicknesses will be difficult to sustain in a thin film reactor without adversely affecting the wettability of the reaction surface and the uniformity of the film. The effects of four main variables (film thickness, UV intensity, initiator concentration, and exposure time) are studied under static film conditions. A 366‐nm wavelength is utilized for the UV radiation with 2,2‐dimethoxy‐2‐phenylacetophenone (Irgacure 651) as the photoinitiator dissolved in n‐butyl acrylate. The molecular weights, polydispersities, and monomer conversions are measured by gel permeation chromatography. In a 400 μm thick film, conversions of >90% can be achieved with an exposure time of 40 s at a radiation intensity of 175 mW/cm². The results using the same polymerization system in the spinning disk reactor are presented and compared with the static film results in Part II of this series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2079–2095, 2004     

Effect of solvents on radiation‐induced grafting of styrene onto fluorinated polymer films

The effect of solvents on radiation‐induced grafting of styrene onto commercial fluorinated polymer films such as poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) and poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) was investigated by a simultaneous irradiation technique. Three solvents, ie methanol, benzene and dichloromethane, were used to dilute styrene under various irradiation doses, dose rates and monomer concentrations. The effect of addition of mineral and organic acids on the degree of grafting in the presence of the three solvents was also studied. The degree of grafting was found to be strongly dependent upon the type of solvent and composition of the monomer/solvent mixture. Dilution of styrene with dichloromethane in various grafting conditions was found to enhance dramatically the degree of grafting compared with other solvents, and the maximum degree of grafting was achieved at a monomer/solvent mixture having a composition of 60:40 (v/v). The formation of polystyrene grafts in the three fluorinated films was verified using FTIR spectrometry. © 2001 Society of Chemical Industry     

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane (MTN) has been achieved with tert‐butyl perbenzoate (TBPB) as initiator in the presence of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy free radical (TEMPO) at 125 °C. The molecular weight polydispersity of the polymers is obviously lower than that of polymers obtained by conventional procedures. As the [TEMPO]/[TBPB] molar ratio increased, the polydispersity decreased and a polydisperty as low as 1.2 was obtained at high TEMPO concentration. With the conversion of the monomer increasing, the molecular weight of the polymers turned higher and a linear relationship between the M_w and the monomer conversion was observed. The monomer conversion, however, did not exceed 30 %. © 2000 Society of Chemical Industry     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. I. Effect of grafting conditions

The simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied at room temperature. The effects of grafting conditions (type of solvent, irradiation dose, dose rate, and monomer concentration) were investigated. The degree of grafting was found to be dependent on the investigated grafting conditions. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be of 0.5 and 1.3 orders, respectively. The results suggest that grafting proceeds by the so‐called front mechanism in which the grafting front starts at the surface of the film and moves internally toward the middle of the film by successive diffusion of styrene through the grafted layers. Some selected properties of the grafted films were evaluated in correlation with the degree of grafting. We found that the grafted FEP films possess good mechanical stability, which encourages their use for the preparation of proton exchange membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 220–227, 2000     

In‐depth characterization of granular starch‐graft‐polyester compositions as obtained by in situ polymerization of lactones from the starch surface

The synthesis of poly(ε‐caprolactone) (PCL)‐grafted granular starch was carried out either in bulk (without solvent) or in toluene suspension by a two‐step procedure. First step relied upon the activation of the hydroxyl groups available at the starch surface by alkylaluminum derivatives like AlEt₃ and removal of non‐surface‐grafted organo‐aluminum active species. The latter species were made free in solution by reaction with the remaining water molecules still contaminating the polymerization medium despite intensive drying of the starch granules. In the second step, ε‐caprolactone was polymerized via a coordination‐insertion ring‐opening polymerization as initiated by the surface‐grafted aluminum alkoxide species. The present contribution aims at investigating various parameters such as nature of the alkyl aluminum activator and monomer (δ‐valerolactone was studied as well), temperature, concentration, and addition of a solvent (polymerization in toluene suspension), reaction time, and also the experimental procedure used to recover the polyester chains and measure the grafting efficiency. It turns out that, under the studied conditions, dialkylaluminum alkoxides surface‐grafted onto the starch granules were more likely generated and promote a fast polymerization reaction with the formation of grafted PCL chains with a molecular weight that can be as high as 225 000 (M_n value) for polymerization carried out in toluene suspension. Copyright © 2004 Society of Chemical Industry     

X‐Ray reflectivity study of polyimide thin films swollen by 1,3‐butadiene and n‐butane

X‐ray reflectivity measurements were performed on two different polyimide thin films synthesized from 2,2‐bis(3,4‐carboxyphenyl)hexafluoropropane dianhydride (6FDA) in 1,3‐butadiene and n‐butane. In 1,3‐butadiene at 2.3 atm, the film thickness increased by 24–30%. However, the film thickness increased by only 10% in n‐butane at 2.3 atm. Excessive increases in film thickness were shown in 1,3‐butadiene, but the decreases in film density were minor. The probability of the condensation of 1,3‐butadiene in the films is indicated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1818–1825, 2000     

Guidelines for dryer design based on results from non‐Fickian model

In polymer solution coatings below the glass transition temperature of the pure polymer, the coating can go undergo a glass transition and develop stresses during drying. When stresses develop, a non‐Fickian model accurately describes solvent mass transport in drying polymer coatings. The non‐Fickian model includes the solvent transport due to both stress and concentration gradients. This article presents a non‐Fickian model, which predicts a lower residual solvent than does the corresponding Fickian model. We showed in an earlier article that the non‐Fickian model predicts trapping skinning (higher residual solvent under more intense operating conditions) at higher drying gas‐flow rates. In this article, the non‐Fickian model was used to investigate how the gas‐flow rate, dry film thickness, and substrate thickness affect the residual solvent for a single‐zone dryer. This work recommends guidelines for choosing gas‐flow rates, gas temperatures, and substrate thickness to minimize the residual solvent. The model predictions show that, at any gas temperature, the residual solvent is minimum at an intermediate gas‐flow rate. The trapping skinning effect is less evident in thicker coatings and substrates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 477–486, 2003     

Improvement of the production of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) terpolyester by manipulating the culture condition

BACKGROUND: The aim of this work is to enhance the production of terpolyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐3HV‐co‐4HB)) produced by a locally isolated bacterium, Cupriavidus sp. USMAA2‐4. The monomer composition was varied by supplementing different carbon precursors and by manipulating the culture condition through one‐stage cultivation. The effect of C/N ratio and different concentrations of carbon source and precursors were investigated in order to produce higher content of this terpolyester. Although research on this biodegradable polyester is abundant, studies on terpolyester P(3HB‐co‐3HV‐co‐4HB) are still limited. RESULTS: Supplementation of oleic acid in accumulation medium increased the bacterial growth and polyhydroxyalkanoate (PHA) accumulation. It was also shown that medium consisting of assorted carbon precursors at C/N 20 gave relatively high dry cell weight and P(3HB‐co‐3HV‐co‐4HB) content. Various compositions of terpolyester were obtained when the concentration of oleic acid and 4HB precursors were manipulated. The combination of oleic acid with γ‐butyrolactone and 1‐pentanol was found to be the best combination to produce high PHA content (81 wt%). The composition of monomer in P(3HB‐co‐3HV‐co‐4HB) was produced in the range 8–13 mol% for 3HV and 9–24 mol% for 4HB, respectively. CONCLUSIONS: The production of P(3HB‐co‐3HV‐co‐4HB) in shake‐flasks successfully produced 81 wt% of PHA content. This manipulated culture condition can be used at larger scale to provide modeling for the production of terpolyester in a bioreactor. Copyright © 2012 Society of Chemical Industry     

Maximum volumetric production of β‐galactosidase by Kluyveromyces fragilis in fed‐batch culture with automatic control

The production of β‐galactosidase by Kluyveromyces fragilis was studied in different culture systems, with dissolved oxygen concentration control and using defined media. An operating strategy of fed‐batch culture with automatic control of substrate addition regulated by dissolved oxygen concentration, consisting of the replacement of variable volumes of broth by fresh medium (once the fed‐batch culture has finished), was designed. The volumetric enzyme productivity (Q_p, 13 600 UI dm^?3 h^?1) obtained was 38% higher than that reached in continuous culture of K fragilis with dissolved oxygen concentration control and far higher than that obtained by batch culture of K fragilis under the same aeration conditions. © 2002 Society of Chemical Industry     

Microporous membranes of isotactic poly(4‐methyl‐1‐pentene) from a melt‐extrusion process. I. Effects of resin variables and extrusion conditions

A study utilizing isotactic poly(4‐methyl‐1‐pentene) (PMP) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial‐stretching) (MEAUS) employed to produce microporous films. The results of this study will be reported in the course of two articles. In this first part, three PMP resins were melt‐extruded into tubular films (blowup ratio; BUR = 1), where the resins each differ in weight‐average molecular weight (M_w). Specific attention was focused upon the morphological and crystal orientation results as a function of the melt‐relaxation times as influenced by the resin characteristics and the processing parameters. The results of a number of melt‐extrusion conditions are presented. A stacked lamellar morphology was obtained in each case; however, the type of stacked lamellar morphology, planar or twisted, and the orientation state was found to depend upon both the resin characteristics, specifically M_w, and the melt‐extrusion conditions. Atomic force microscopy and wide‐angle X‐ray scattering (WAXS) were the main techniques utilized to study the melt‐extruded films, while oscillatory shear measurements, in conjunction with a Carreau–Yasuda analysis, aided in differentiating the melt‐flow behavior of the three resins. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2095–2113, 2002     

Synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid

Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Plasma‐polymerized hexamethyldisiloxane films characterized by variable‐energy positron lifetime spectroscopy

Nanometer‐size holes in plasma‐polymerized thin films were characterized by variable‐energy positron lifetime spectroscopy for the first time. Hexamethyldisiloxane (HMDSiO) was plasma‐polymerized at different discharge powers (30–105 W) and monomer pressures (1.0–4.9 Pa). The positron lifetime spectra of deposited films were collected at positron energies of 1 and 5 keV. All films showed a well‐defined long‐lived component due to pick‐off annihilation of ortho‐positronium (o‐Ps). The o‐Ps lifetime τ₃, reflecting the average size of free‐volume holes in the film, increased with an increasing ratio of plasma discharge power, W, and monomer flow rate, F. Based on the empirical relationship between the o‐Ps lifetime and the cavity radius, hole volumes were estimated to be 0.19–0.36 nm³. We also found that the o‐Ps intensity, I₃, depends strongly on the same parameter, W/F. Comparison with infrared (IR) absorption spectroscopy data showed that Ps formation is suppressed in films with fewer organic bonds and higher disorder, i.e., those increasingly inorganic in nature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2522–2528, 1999