The effect of humidity on water sorption in photoresist polymer thin films

A quartz crystal microbalance technique has been utilized to measure water sorption and desorption in three photoresist polymers: poly(p-hydroxystyrene), novolac, and bis-triflouromethyl carbinol substituted poly(norbornene). The humidity of the sample environment was varied to determine the rate and amount of water absorbed into the photoresist thin films as a function of local environmental conditions. At 100% absolute humidity, the polymers were found to absorb 9.8, 2-3, and 5-8 wt%, respectively. The sorption and diffusion of water into the polymer thin films was observed to initially follow Fickian behavior in the low fractional mass uptake regions (M_t/M_∞<0.6), but concentration dependent diffusion behavior was seen at higher levels of water uptake. All films sorbed and desorbed water rapidly with the majority of the water uptake or loss occurring in the first few seconds of exposure.     

Electrochemical and thermal properties of polymer electrolytes based on poly(epichlorohydrin-co-ethylene oxide-co-ally glycidyl ether)

A series of novel electrolytes based on the terpolymer host, poly(epichlorohydrin-co-ethylene oxide-co-allyl glycidyl ether) with lithium perchlorate and lithium bis(trifluoromethanesulfonyl)imide have been prepared and characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode and thermal analysis.Electrolyte compositions, represented as p(EEO-AGE)LiX(wt%), were produced with lithium salt compositions between 0.5 and 53 wt% (where wt% indicates amount of lithium salt present in the epichlorohydrin-co-ethylene oxide-co-allyl glycidyl host matrix). The guest salt and host polymer were dissolved in tetrahydrofuran and cast to produce thin, free-standing electrolyte films.The p(EEO-AGE)LiX(wt%) (X = ClO₄ and TFSI) electrolytes showed encouraging levels of ionic conductivity and acceptable thermal stability. Electrolytes based on this host polymer were obtained as completely amorphous films with good mechanical properties.     

Vapor sorption in thin supported polymer films studied by white light interferometry

In the present study, we apply a white light interferometric methodology to study sorption of moisture and methanol vapor in thin films of poly(2-hydroxyethyl methacrylate) [PHEMA] and poly(methyl methacrylate) [PMMA], supported on oxidized silicon wafers. The measured equilibrium thickness expansion of each film, exposed to different activities of the vapor penetrant, is used to determine the sorption isotherm of the system. Results for relatively thick films (100 nm < L_o < 600 nm) are compared with corresponding literature data for bulk, free-standing films, obtained by direct gravimetric methods. Furthermore, PMMA films of thicknesses lower than 100 nm were employed in order to study the effect of the dry film's thickness, and of substrate, on fractional swelling.     

Effects of film thickness on moisture sorption, glass transition temperature and morphology of poly(chloro-p-xylylene) film

Moisture sorption, glass transition temperature (T_g) and morphology of ultra thin poly(chloro-p-xylylene) (parylene-C) are greatly influenced by geometrical confinement effects. For film <50 nm, the equilibrium moisture saturation is a decreasing function of film thickness. However, the T_g of film <50 nm is about 10 °C higher than thicker films. The above phenomena are attributed to the effect of geometrical confinement on the thermal properties and the morphology of parylene-C film. Surface confinement results in an increased in T_g, but a decreased in crystallinity for films <50 nm. In this study, we show that the increase in moisture sorption for parylene-C films <50 nm is dominated by the crystallinity variation.     

Preparation and structure characterization of hairy nanoparticles consisting of hydrophobic core and thermosensitive hairs

Structural characterization of hairy nanoparticles consisting of poly(styrene-co-glycidyl methacrylate) (St/GMA) core and poly(NIPA-co-vinylimidazole) (NIPA/VIm) hair has been carried out by dynamic light scattering. The hairy molecules were introduced by surface graft-polymerization of a mixture of NIPA and VIm monomers to the St/GMA core particles with the hydrodynamic radius R_H of 135±10 nm. The R_H of St/GMA-core-NIPA/VIm-hair particles was R_H=360±20 nm at 20 °C, which gradually decreased to 285±10 nm by heating to 33.0 °C, and then underwent a sharp decrease to 175±10 nm by further heating to 33.8 °C. The final value went to 159±10 nm at 36 °C. This decrease in R_H is due to the shrinking transition of NIPA/VIm chain by hydrophobic association. The degree of shrinking of the hairy particles is compared with that of bulk NIPA gels from the viewpoint of geometrical constraints.     

In situ monitoring of thermal transitions in thin polymeric films via optical interferometry

A novel, low-cost, rapid, accurate, non-invasive and high throughput method based on the principles of Optical Interferometry (OPTI method) has been developed and applied for the in situ monitoring in one simple run of first (melting) and second (glass transition) order transitions as well as of the thermally induced decomposition of various thin polymeric films spin coated on flat reflective substrates (untreated silicon wafers). The new method has been applied successfully for measuring the glass transition, melting and decomposition temperatures of six commercially available polymers [poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate), (PHEMA), poly(vinyl acetate-co-crotonic acid), (PVACA), poly(vinyl pyrrolidone) (PVP), poly(vinyl chloride-co-vinyl acetate) (PVCVA) and crystalline poly(vinylidene fluoride-co-hexafluoropropylene) (PVFHP)] of known T_gs or T_ms. The recorded interferometric signals were identified and characteristic signal patterns were qualitatively correlated to specific transitions. The monitoring of first and second order transitions in thin polymeric films is based on detectable differentiations of the total energy of a fixed wavelength laser beam incident almost vertically (angle of incidence <5°) onto a thin polymeric film spin coated on a flat reflective substrate. These differentiations are caused by film thickness and/or refractive index changes of the polymeric film both resulted from the significant change of the polymer's free volume taking place on the transitions. For film thicknesses over approx. 200-250 nm, the T_g or T_m of the polymeric films measured with the OPTI method were in excellent agreement with the corresponding values of the polymer, measured by DSC. An investigation on the trends of the T_g of PHEMA and PMMA films in a wide thickness range (30-1735 nm) was also carried out. Ultra-thin (∼30 nm) films of PMMA and PHEMA showed significant increase in their T_g values by approx. 30 °C upon comparing to their corresponding bulk T_gs. This behavior was attributed to an enhanced polymer-surface interaction through hydrogen bonding and/or to changes in the tacticity of the polymer.     

Determination of reactivity ratios and swelling characteristics of ‘stimuli’ responsive copolymers of N-acryloyl-N′-ethyl piperazine and MMA

‘Stimuli’ responsive copolymers of N-acryloyl-N′-ethyl piperazine (AcrNEP) and methyl methacrylate (MMA) were synthesized by free radical solution polymerization. The copolymers were analyzed as thin films by FTIR spectroscopy. The monomer reactivity ratios were determined by linearization methods of Fineman-Ross (F-R) and Kelen-Tüdös (K-T) giving the results r₁ (AcrNEP)=0.58 and r₂ (MMA)=0.91 by the F-R method and r₁=0.72 and r₂=1.08 by the K-T method. The latter r values in turn yielded Q=0.59 and e=−0.12 for AcrNEP. Crosslinked copolymer hydrogels of AcrNEP and MMA with various compositions were prepared in bulk and solution by photo-initiated free-radical polymerization. The gels were dual responsive to pH and temperature. The response to pH was reversible with a response time of 100 min with good reversibility and with no loss in swelling capacity. Water sorption of the gels was investigated gravimetrically and the collective diffusion coefficients were determined at 10, 25, and 50 °C. The water sorption of the gels in water was Fickian. The temperature dependence of the equilibrium water content was studied by the Gibbs-Helmholtz equation. The enthalpy of mixing decreased with an increase in the hydrophilic content (AcrNEP) of the gel. Other parameters such as type and amount of crosslinker, preparative conditions, nature of buffers, and salts were found to influence the swelling behavior.     

Extension of a compressible lattice model to CO2 + cosolvent + polymer systems

We have recently proposed a compressible lattice model for CO₂ + polymer systems in which CO₂ forms complexes with one or more functional groups in the polymer. Furthermore, we have shown that this model is able to simultaneously correlate phase equilibria, sorption behavior, and glass transition temperatures in such systems. In the present work, we extend the model to ternary CO₂ + cosolvent + polymer systems and demonstrate that cloud point behavior in CO₂ + dimethyl ether + poly (?-caprolactone), CO₂ + dimethyl ether + poly (isopropyl acrylate), and CO₂ + dimethyl ether + poly (isodecyl acrylate) systems can be predicted using parameters obtained from binary data. Our results also suggest that dimethyl ether may form weak complexes with poly (?-caprolactone), poly (isopropyl acrylate), and poly (isodecyl acrylate).     

Synthesis and properties of thermosensitive, crown ether incorporated poly(N-isopropylacrylamide) hydrogel

A crown ether derivative (4′-allyldibenzo-18-crown-6, CE) was covalently incorporated into the network of temperature sensitive poly(N-isopropylacrylamide) (PNIPA) hydrogels by copolymerization in a mixed solvent of water and tetrahydrofuran (H₂O/THF). The poly(N-isopropylacrylamide-co-4′-allyldibenzo-18-crown-6) (poly(NIPA-co-CE)) hydrogels exhibited dramatically faster deswelling rates than normal PNIPA hydrogels at a temperature (50 °C) above their lower critical solution temperatures. The effect of the solvent component ratio in the mixed solvent during the copolymerization on the swelling properties of the poly(NIPA-co-CE) hydrogel was investigated. The thermosensitive poly(NIPA-co-CE) hydrogels have potential applications in the extraction of cations and separation of chiral drugs.     

Effect of acrylic acid on the physical properties of UV-cured poly(urethane acrylate-co-acrylic acid) films for metal coating

UV-cured poly(urethane acrylate-co-acrylic acid) (PU-co-AA) films with five different compositions were prepared by reacting isophorone diisocyanate (IPDI), polycaprolactone triol (PCLT), 2-hydroxyethyl acrylate (HEA), and different weight ratios of trimethylolpropane triacrylate (TMPTA) and acrylic acid (AA) as diluents. Their synthesis and physical properties including gel content, adhesion properties, morphological structure, thermal properties, and mechanical hardness were investigated as a function of the AA content. It was found that the physical properties of the PU-co-AA films are strongly dependent upon the AA content. Crosscut tests showed that PU-co-AA films with lower AA content showed 0% adhesion (0B), and the adhesion of films increased dramatically as the AA content increased to 40–50%. The pull-off measurements showed that the adhesion force of the PU-co-AA films to stainless steel substrates varied from 6 to 31 kg_f/cm² and increased linearly with increasing AA content. PU-co-AA films with higher AA content can be good candidates for UV-curable coating of metal substrates such as stainless steel. However, the thermal stabilities and mechanical hardness decreased with increasing AA content, which results from the relatively linear and flexible structure of AA.     

Structures and cocrystallization behavior of copolyesters based on poly(octamethylene terephthalate) and poly(octamethylene 2,6-naphthalate)

We have synthesized poly(octamethylene terephthalate) (POT), poly(octamethylene 2,6-naphthalate) (PON), and poly(octamethylene terephthalate-co-octamethylene 2,6-naphthalate)s [P(OT-co-ON)s] with various comonomer composition by melt-polycondensation reaction and investigated their chain structures, crystalline structures, melting and cocrystallization behavior by using ¹H NMR spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively. It was observed that P(OT-co-ON)s exhibit clear melting and crystallization peaks in DSC thermograms and sharp diffraction peaks in WAXD patterns throughout the copolymer composition, resulting from the cocrystallization behavior of OT and ON units in copolymers. When the melting and crystallization temperatures of P(OT-co-ON)s are compared as a function of the copolymer composition, there exists an eutectic point at around 23 mol% ON, where the crystal transformation from POT-type to PON-type occurs. It was confirmed from WAXD patterns of the melt-crystallized samples that the crystal transformation from POT-type to PON α-type to PON β-type occurs with the increment of the comonomer ON content in copolymers, i.e., POT-type crystals for POT and P(OT-co-ON) with 11 mol% ON, PON α-type crystals for P(OT-co-ON)s with 23-48 mol% ON, and PON β-type crystals for PON and P(OT-co-ON)s with 62-87 mol% ON. Both DSC and WAXD results demonstrate the isodimorphic cocrystallization of P(OT-co-ON)s. Based on the Wendling-Suter model for cocrystallization thermodynamics, it was found that the average defect free energy for the inclusion of OT units into PON β-type crystals is much lower than the value of the incorporation of ON units into POT-type crystals.     

Water vapor barrier property of organic-silica nanocomposite derived from perhydropolysilazane on polyvinyl alcohol substrate

Poly(vinyl alcohol) membrane was coated with organic-silica nanocomposite derived from perhydropolysilazane. For organic composite part, polystyrene-block-poly(4-vinyl phenol) [SP], poly(tert-butyl acrylate-co-2-hydroxyethyl methacrylate) [BA] and poly(butyl methacrylate-co-2-hydroxyethyl methacrylate) [BMA] were used. Water vapor barrier property of coat membrane was measured at relative humidity = 96% by a cup method. The coat films of nanocomposites with SP-silica and BA-silica showed better water vapor barrier property than those of the silica coat film without organic polymer and BMA-silica composites. The surface morphologies of the coat films were investigated by scanning electron microscopy and atomic force microscopy. The addition of organic polymer to silica prevented the crack formation of coat layer on the substrate.     

Monitoring of swelling of interpenetrating polymer network of polyethylene/poly(styrene-co-butylmethacrylate) (PE/P(S-co-BMA)) in toluene and cyclohexane using fluorescence spectroscopy

A real-time monitoring of excimer emission fluorescence probe di(1-pyrenemethyl)ether (DiPyM) was used for study swelling interpenetrating polymer network (IPN) consisting of polyethylene/poly(styrene-co-butylmethacrylate) (PE/P(S-co-BMA)) and containing different network density. DiPyM was introduced into IPN during polymerisation or was penetrated into blocks from toluene solution. The effect of solvent quality for swelling of IPN and density of IPN network was also studied. From steady-state measurements of monomer and excimer emission ratio (I_e/I_m), no difference was found between rate of swelling IPN with 0.5, 1 and 3 mol% of cross-linker. The rate of IPN swelling seems to be rather high. Some differences was found at real-time monitoring of excimer emission (λ_em=495 nm) of DiPyM measured during desorption of DiPyM from swelled IPN blocks. At higher content of cross-linker, a slower rate of DiPyM desorption from IPN matrix was observed.     

Corrosion inhibition of stainless steel by polyaniline,poly(2-chloroaniline), and poly(aniline-co-2-chloroaniline) in HCl

Polyaniline (PANi), poly(2-chloroaniline) (PClANi), and poly(aniline-co-2-chloroaniline) (co-PClANi) films were synthesized by electrochemical deposition on 304-stainless steel (SS) from an acetonitrile solution. The structural properties of these polymer films were characterized by spectroscopic (FTIR and UV–vis) and electrochemical (cyclic voltammetry) methods. Open circuit potential–time (E_ocp–time) curves, potentiodynamic polarization, and electrochemical impedance (EIS) measurements showed that these films have significant protective performance against corrosion of SS in 0.5 M HCl solution. It was found that co-PClANi film has acted as a passivator as well as barrier for cathodic reduction reaction in a similar manner as PANi film. However, PClANi film has behaved only as barrier for corrosion protection of SS in 0.5 M HCl.     

Polymorphism of syndiotactic poly(p-fluoro-styrene)

Syndiotactic poly(p-fluoro-styrene) (s-PPFS) has been prepared with a polymerization procedure which allows reaching high average molecular masses and satisfactory yields. The polymorphic behavior of the polymer has been mainly studied by X-ray diffraction, calorimetric and infrared analyses. The main crystalline phase of s-PPFS, obtained by melt processing or cold-crystallization, exhibits trans-planar chains, is orthorhombic (a = 9.5 Å, b = 28.7 Å, c = 5.1 Å) and melts at nearly 320 °C. The X-ray analysis shows a strict analogy of this orthorhombic phase with the β phase of s-PS, also as for the occurrence of two limit ordered (β″) and disordered (β′) modifications, which differ for the intensity of reflections characterized by h + k = 2n + 1. A metastable crystalline phase, also exhibiting trans-planar chains, has been observed for as-polymerized samples as well as for amorphous samples crystallized by sorption of toluene or 1,4-difluoro-benzene. Mainly on the basis of solvent sorption and desorption experiments, it is suggested that this metastable phase is a co-crystalline phase with the low-molecular-mass guest molecules.     

Cocrystallization behavior of poly(hexamethylene terephthalate-co-hexamethylene 2,6-naphthalate) random copolymers

A series of poly(hexamethylene terephthalate-co-hexamethylene 2,6-naphthalate) (P(HT-co-HN)) random copolymers were synthesized by melt polycondensation and characterized using ¹H NMR spectroscopy and viscometry. Their cocrystallization behavior was investigated using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) method. Even though the P(HT-co-HN) copolymers synthesized are statistically random copolymers, they show a clear melting and a crystallization peak in DSC thermograms over the entire range of copolymer composition and have a minimum melting temperature in the plot of melting temperature versus copolymer composition. WAXD patterns of all the copolymer samples show sharp diffraction peaks and are largely divided into two groups, i.e. PHT type and PHN type crystals. In addition, WAXD patterns of the PHN type crystals are subdivided into two types of PHN α and PHN β according to the copolymer composition. These facts indicate that the P(HT-co-HN) copolymers show isodimorphic cocrystallization. The composition at which the crystal transition between PHT type and PHN type occurs is equivalent to the eutectic composition (22 mol% HN content) for the melting temperature. When the defect free energies were calculated by using the equilibrium inclusion model proposed by Wendling and Suter, the defect free energies in the case of incorporation of HT units in the PHN α and β crystals were higher than the case of incorporation of HN units in the PHT crystal lattice.     

Synthesis and characterization of temperature-responsive copolymer of PELGA modified poly(N-isopropylacrylamide)

Novel amphiphilic PELGA modified temperature-responsive copolymer, [(poly(methoxyethylene glycol)-co-poly(lactic acid)-co-poly-(glycolic acid))acrylate-co-poly(N-isopropylacrylamide)-co-poly(N-hydroxymethylacrylamide)] (PELGAA-co-PNIPAAm-co-PNHMAAm) was synthesized by incorporating PELGA as the amphiphilic moiety into poly(N-isopropylamide) with various LA/GA ratios. Polymers obtained were characterized by FT-IR, GPC, ¹H-NMR and DSC. The lower critical solution temperature (LCST) of the copolymeric nanoparticles was 40±0.6 °C, the critical aggregation concentration (CAC) was 18 mg L⁻¹, and reversible change in nanoparticle size related to temperature was fluctuated between 210±10 and 109±26 nm, while change in zeta potential of the nanoparticles was between −36±6 and −26±4 mV. The transmission electron microscopy (TEM) images of nanoparticles were also presented.     

Physical and functional characterization of PHASCL membranes

Dense semicrystalline membranes of polyhydroxyalkanoates with medium change length (PHA_SCL), polyhydroxybutyrate (PHB) and poly β (hydroxybutyrate-co-hydroxyvalerate) [P(βHB-co-XβHV)] were characterized using wide-angle X-ray (WAXS) and scanning electron microscopy. PHB membranes showed a more rugged surface than those of copolymers (0-22%HV). Properties such as swelling capacity, vapor permeability and selectivity were investigated. Swelling percentage in water-ethanol mixtures was 34% for PHB as compared to 14% for copolymers membranes. The ethanol/water selectivity (α_s) of PHB was 5.8 which shows that it is more selective than copolymers.The water vapor and ethanol vapor permeability were determined by a gravimetric technique at different temperatures by static and dynamic methods. PHB permeability was 69.5 Barrer at 30 °C and a discreet increment was observed at temperatures (30-50 °C). The difference in permeability between PHB and [P(βHB-co-X%βHV)] could be interpreted in terms of the crystallization rate, crystallite size and distribution which impact to transport properties of amorphous phase.     

Synthesis and characterization of chiral polythiophenes: Poly [(R)-(−) and (S)-(+)-2-(3′-thienyl)ethyl N-(3″,5″-dinitrobenzoyl)-α-phenylglycinate]

(R)-(−) (1) and (S)-(+)-2-(3′-Thienyl)ethyl N-(3″,5″-dinitrobenzoyl)-α-phenylglycinate (2) monomers were synthesized, characterized, and polymerized in chloroform using FeCl₃ as an oxidizing agent. Molecular weights of 2.6 × 10⁴ and 3.2 × 10⁴ for poly1 and poly2, respectively, were determined by SEC analysis. FTIR spectra of the polymers indicated the coupling of monomers through the α positions. UV-vis spectra showed absorption bands at λ_max = 226 and 423 nm for poly1 and poly2, ascribed to transitions of side groups and polythiophene backbone, respectively. Poly1 and poly2 remained stable up to 210 °C. At higher temperatures, a two step weight loss degradation process was observed for both polymers by TGA analysis. ¹H NMR, in the presence of Eu(tfc)₃, and optical rotation measurements indicate the chiral properties of the monomers 1 ([α]_D²⁸ = −76.2) and 2 ([α]_D²⁸ = +76.0), and the maintenance of chirality after polymerization (poly1 [α]_D²⁸ = −29.0 and poly2 [α]_D²⁸ = +28.4, c = 2.5 in THF). According to scanning electron microscopic analysis, the polymers are highly porous.     

Influence of ionic aggregation on the surface energies of crystallites in poly(butylene terephthalate) ionomers

The influence of ionic comonomer units and ionic aggregation on the crystallization behavior and crystallite surface energies of poly(butylene terephthalate-co-5-sodiosulfoisophthalate) (PBTi) ionomers containing 3 and 5 mol% dimethyl-5-sodiosulfoisophthalate monomer units is compared to that of pure poly(butylene terephthalate). The rate of crystallization of the ionomers, as determined from an Avrami analysis, was shown to decrease with an increase in the ionic comonomer unit content. This behavior was attributed to the presence of non-crystallizable comonomer units and the reduced mobility of the crystallizable chain segments due to ionic aggregation in the PBT ionomers as evidenced by the broad peak centered about −9.5 ppm in the ²³Na NMR spectrum. The surface free energies of the polymer crystallites were determined using the Avrami rate constants in a modified Laurizten-Hoffman method. The PBT ionomers showed a 35-70% increase in the product of the surface energies (σσ_e) over that observed for pure PBT. By assuming a constant lateral surface energy, this behavior was attributed to a 30-70% increase in the work associated with chain folding. Relative to crystallites formed in pure PBT, these data suggest that there is a more disordered crystalline fold surface in the ionomers due the perturbed development of crystallites in the presence of a strong electrostatic network.