Characterization of UV-irradiated Lexan polycarbonate films

Lexan polycarbonate films were irradiated by UV radiation at wavelength $ \lambda $  = 250 nm under different time exposures of 1, 2, 4, 6 and 7 h. Structural, optical and mechanical modifications were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), UV–Visible spectroscopy, impedance analysis, tensile testing and rheometry methods. The crystallite size and percentage of crystallinity were found to decrease upon irradiation as was studied by XRD. It indicated that polymer was moving towards more disordered state after irradiation corroborating DSC results. FTIR Study showed the carbonate linkage is the radiation-sensitive linkage and benzene ring does not undergo any change after irradiation. SEM results showed the formation of pores after irradiation. The atomic force microscopy measurements revealed that the average roughness of the film increased after being irradiated. The glass transition temperature was observed to decrease after irradiation as revealed by DSC measurement. UV–Visible spectra showed decrease in optical band gap after irradiation due to chain scission in the Lexan polycarbonate. Plot of AC conductivity versus log (f) displayed a sharp increase in conductivity at higher frequencies and dielectric constant/loss was observed to change with the irradiation time. The mechanical properties and average molecular weight of Lexan polycarbonate decreased after irradiation, while the average number of chain scissions per original polymer molecule increased with increase in time of exposure.     

Different photodegradation processes of PVC with different average degrees of polymerization

The influence of ultraviolet (UV)‐irradiation on the photodegradation mechanism of different average degrees of polymerization (DP ) of poly(vinyl) chloride (PVC) with UV‐irradiation time was investigated by viscosity‐average molecular weight determination, UV‐vis spectroscopy, Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), contact angle measurement, and scanning electron microscopy (SEM). PVC films with different DP (800, 1000, 1300, 3000) were prepared by solution casting. It was carried out exposing specimens to a xenon‐arc light source with a spectral irradiance of 0.68 W/(m² ·nm) at 63°C. It was found that the photodegradation mechanism of the lower DP of PVC (DP = 1000) was different from the higher DP of PVC (DP = 3000). This was because the lower DP of PVC was a homopolymer, while the higher DP of PVC was often produced by copolymerizing with a certain quantity of crosslinking agent (e.g., DAP and DAM). UV‐vis and FTIR spectroscopy studies provided some results concerning the structure of the irradiated PVC, and the carbonyl index and C? Cl index were induced to study the process of PVC photodegradation with different DP . TGA showed that the degradation temperatures of different weight loss increased with the irradiation time. The surface morphology of the irradiated polymer films with different DP was observed by contact angle measurement and SEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Free volume‐related microstructural properties of lithium perchlorate/sodium alginate polymer composites

The effect of salt (LiClO₄) on free volume‐related microstructural, optical, and dielectric properties of lithium perchlorate (LiClO₄)‐doped sodium alginate (NaC₆H₇O₆)_n solid polymer electrolyte were studied using Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), UV–Visible, dielectric measurements, and positron annihilation lifetime spectroscopy (PALS) techniques. The FTIR study reveal that the LiClO₄ interact with the O H groups of sodium alginate (NaAlg) and forms charge transfer complex (CTC). These formed CTC within the composite film affect the optical property of the polymer composite, which was reflected from UV–Visible study. The free volume was probed by the PALS technique, which uses the o‐Ps pickup lifetime τ _3, as an indication of local electron density and mean free volume radius. The o‐Ps pickup intensity I₃, reflects the probability of o‐Ps formation. The o‐Ps components τ₃ and I₃ increases with salt concentration, which shows microstructural modifications due to the decrease in the crystallinity of the NaAlg as observed from XRD studies. Therefore, electrical studies on the doped NaAlg reveal that the ionic movement in the composites is mainly due to the segmental motion of the polymer backbone. So, the complex formation due to doping affects the free volume‐related microstructure and hence the dielectric properties including the AC conductivity of the polymer composites. POLYM. COMPOS., 35:1267–1274, 2014. © 2013 Society of Plastics Engineers     

Dopant‐induced microstructural,optical, and electrical properties of TiO2/PVA composite

The optical, electrical, and microstructurtal properties of pure and TiO₂/Poly(vinyl alcohol) (PVA) composite polymer films were carried out using FTIR, XRD, UV‐Visible, DC electrical conductivity, and Positron annihilation lifetime spectroscopy (PALS) techniques. The FTIR study reveals that the Ti⁺ ions of TiO₂ interacts with the OH groups of PVA via intra/inter molecular hydrogen bonding and forms charge transfer complex (CTC). These formed CTC will affect the optical property of the composite film, which is reflected from UV‐Visible study. Using the observed UV–Visible spectra, optical energy band gap is estimated and its value decreases with increasing dopant concentration. The positron annihilation studies show that the considerable effect on free volume related microstructure of the PVA due to doping and complex formation. These microstructural modifications are also enhances PVA crystallinity which is reflected from XRD studies. It is also observed that the TiO₂ particle forms cluster within the PVA due to the aggregation of particles and these particle cluster size increases with dopant concentration. These microstructural variations due to doping affects the DC electrical conductivity and its variations are understood based on the intra chain one‐dimensional interpolaron hopping conduction mechanism. POLYM. COMPOS. 37:987–997, 2016. © 2014 Society of Plastics Engineers     

Influence of UV absorber on photodegradation processes of poly(vinyl chloride) with different average degrees of polymerization

The influence of UV absorber (Chimassorb81) on the photodegradation mechanism of different average degrees of polymerization (DP ) of poly (vinyl chloride) (PVC) with UV‐irradiation time was investigated by viscosity‐average molecular weight determination, UV‐vis spectroscopy, FTIR, contact angle measurement, and scanning electron microscopy (SEM). The PVC films with different DP (1000 and 3000), which contained 0.3 or 0.5 phr Chimassorb81, were prepared by solution casting. It was carried out by exposing specimens to xenon‐arc light source with a spectral irradiance of 0.68 W/(m² nm) at 63°C. It is found that the Chimassorb81 is efficient photostabilizer for PVC with different DP . Although the Chimassorb81 delays the photodegradation of PVC, it does not influence the photodegradation mechanisms of PVC with different DP . The main photodegradation reaction for the lower DP of PVC is dehydrochlorination in the initial stage of UV‐irradiation, and then the crosslinking and chain scission reactions occurred after long irradiation. However, the main reaction of the higher DP of PVC is not dehydrochlorination but crosslinking and chain scission in the initial stage of UV‐irradiation. The results of carbonyl index, C? Cl index, contact angle measurement, and SEM also show that the photostability of Chimassorb81 is more effective for the higher DP of PVC, especially in the presence of higher concentration of Chimassorb81. POLYM. ENG. SCI., 47:1480–1490, 2007. © 2007 Society of Plastics Engineers     

Synthesis,characterization, and self‐assembly of cationic coumarin side‐chain polymer

In this study, the synthesis of a novel cationic coumarin‐containing polymer (C‐CPA) was presented. C‐CPA was examined optically using photoluminescence (PL) spectroscopy. The optical data suggested that they were promising blue‐emitting materials mainly due to the coumarin chromophore on the side chain. Moreover, the synthesized cationic polymer was suitable for layer‐by‐layer electrostatic self‐assembly thin film deposition from dilute polymer solution and multilayers were fully characterized by UV–vis spectroscopy, PL spectroscopy and atomic force microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An ionic liquid‐based polymer with π‐stacked structure as all‐solid‐state electrolyte for efficient dye‐sensitized solar cells

An ionic liquid based polymer, poly(1‐ethyl‐3‐(acryloyloxy)hexylimidazolium iodide) (PEAI), was synthesized and employed as electrolyte to fabricate all‐solid‐state dye‐sensitized solar cells. The photophysical properties of PEAI were studied by UV–vis absorption spectroscopy and photoluminescence spectroscopy. PEAI exhibited significant hypochromism and red shift in UV–vis absorption spectra and large Stokes shifts in photoluminescence spectra, indicating the formation of a novel π‐stacked structure in which the imidazolium rings in the side chain were stacked. Without iodine in its preparation, DSC with PEAI electrolyte achieved a conversion efficiency of 5.29% under AM 1.5 simulated solar light irradiation (100 mW cm^?2). The side‐chain imidazolium π‐π stacking in PEAI played a key role in the holes transport from the photoanode to the counter electrode. Both the open‐circuit voltage and short‐circuit current density showed decreases with the increase in the content of iodine in PEAI electrolyte. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of PS‐PMMA/ZnO nanocomposite films with novel properties of high transparency and UV‐shielding capacity

High transparent and UV‐shielding poly (styrene)‐co‐poly(methyl methacrylate) (PS‐PMMA)/zinc oxide (ZnO) optical nanocomposite films were prepared by solution mixing using methyl ethyl ketone (MEK) as a cosolvent. The films were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectra, high‐resolution transmission electron microscopy (HR‐TEM), and atomic force microscope (AFM). Cross‐section HR‐TEM and AFM images showed that the ZnO nanoparticles were uniformly dispersed in the polymer matrix at the nanoscale level. The XRD and FTIR studies indicate that there is no chemical bond or interaction between PS‐PMMA and ZnO nanoparticles in the nanocomposite films. The UV–vis spectra in the wavelength range of 200–800 nm showed that nanocomposite films with ZnO particle contents from 1 to 20 wt % had strong absorption in UV spectrum region and the same transparency as pure PMMA‐PS film in the visible region. The optical properties of polymer are greatly improved by the incorporation of ZnO nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of polycarbonate‐co‐poly(p‐ethylphenol) and CdS nanocomposites

The enzyme‐catalyzed synthesis of poly(p‐ethylphenol) (PEP) was modified by copolymerization with polycarbonates through triphosgene at low temperature to form polycarbonate‐co‐poly(p‐ethylphenol) (PC‐co‐PEP). FTIR, NMR, GPC, and thermal analysis verified the formation of PC‐co‐PEP. The copolymers have an optical absorption in the UV range. CdS semiconductor nanocrystallites were synthesized in reversed micelles with subsequent in situ enzymatic copolymerization of p‐ethylphenol and 4‐hydroxythiophenol in the same medium. TEM and ATR–FTIR showed that the polymer precipitated in spherical morphologies, incorporating CdS nanocrystals into the polymer matrix, with surface hydroxyl groups. The polymer/CdS core was then dispersed into polycarbonate. The polymer/CdS nanocomposites showed higher optical aborbance in the UV‐vis range when compared to the polymer matrix without CdS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1851–1868, 1999     

Optical and electrochemical properties of thermostable polymers containing light‐emitting units

Two series of polymers and copolymers containing oxadiazole units have been studied with respect to their photo‐optical and electrochemical behavior. Fluorene units were introduced in the macromolecular chain together with oxadiazole rings in order to obtain a better balance between electrons and holes injection and transporting properties. Upon irradiation with UV light the polymers showed photoluminescence maxima in the blue spectral range. Cyclic voltammetry was performed in order to obtain information about the electrochemical stability and reversibility of the redox processes of these polyoxadiazoles. The highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels, and electrochemical and optical band gap values were calculated by using the results of cyclic voltammetry and UV/vis spectroscopy, respectively, showing very good electron injection and transport characteristics. POLYM. ENG. SCI., 54:1126–1133, 2014. © 2013 Society of Plastics Engineers     

Structural alterations of polycarbonate/PBT by gamma irradiation for high technology applications

In this work, polycarbonate/polybutylene terephthalate (PC/PBT) was irradiated with different gamma doses ranging from 200 kGy to 1950 kGy. Structural alterations of irradiated PC/PBT polymer blend have been studied using UV–vis spectroscopy, X-ray diffraction, and Fourier transform infrared (FTIR), as well as surface wettability. The results of UV–vis spectra showed that gamma irradiation induced an increase in the optical absorption with an increase in the gamma doses with shift in the optical absorption edge in the irradiated samples toward the higher wavelength. This shift is correlated with the decrease in optical band gap energy. Optical band gap decreases up to 12 and 20% with respect to pristine sample for direct and indirect transition, respectively. The number of carbon atoms per conjugated length has been estimated. The α phase and β phase of the crystalline PBT structure were observed. The α phase reflections are slightly increased due to the irradiation but the accompanying α to β transformation alters the results. FTIR investigation showed slight variation in the absorption spectrum specially in the range from 1300 to 1001 cm^?1 which are related to the O–C–O arrangements that is found to be the most affected part of the molecule by irradiation. A remarkable increase was observed in the wettability, surface free energy, and adhesion work of irradiated samples with an increase in the gamma doses.     

Influence of ion-irradiation on the free volume controlled diffusion process in polycarbonate—a positron lifetime study

Iodine sorption in un-irradiated and ion-irradiated polycarbonate (PC) has been investigated using positron lifetime spectroscopy. The decrease in positron lifetime parameters of ion-irradiated sample is attributed to the free volume modifications, and the formation of more stable free radicals on cross-linking. The difference UV absorption spectrum shows a strong absorption peak at 384 nm which is due to 2,2′-dihydroxybenzophenone; this depicts the possibility of photo stabilisation of polycarbonate on ion-irradiation. A comparative study of sorption process is explained in terms of iodine diffusion in free volume holes in un-irradiated and ion-irradiated polycarbonates. The experimental results on iodine diffusion shows an early saturation of positron parameters in irradiated PC, which is due to an increase in the rate of diffusion as small number of bigger size free volume holes are formed on irradiation. The diffusion process follows Fick's law and, an exponential type of correlation has been observed between fractional free volume and diffusion coefficient which indicates that Fujita's free volume theory is valid before and after ion-irradiation.     

Preparation and optical performance of chiral polymers having azobenzene segments

A series of monomeric azobenzene derivatives of 6‐(4‐nitro‐4′‐oxy‐azobenzene acrylate with carbon numbers of 6 and 11, and the chiral monomer of bornyl 4‐(6‐acryloyloxyhexyloxy)‐phenyl‐4′‐benzoate were synthesized. Chiral polymers having bornyl group end‐capped pendants with azobenzene‐derived segments were prepared. Molecular structures and polymer compositions were confirmed by using ¹H‐NMR, elemental analysis, FTIR, and UV–vis analyzers. Thermodynamic properties of both monomers and polymers were investigated. Specific rotations of chiral monomers and polymers were estimated by using an automatic digital polarimeter. Liquid crystalline textures of monomers and polymers were analyzed by using a polarizing optical microscope and confirmed by a small‐angle X‐ray analyzer. The optical reflection characteristics of composite cells with chiral nematic liquid crystal and various amounts of azobenzene derivatives were evaluated by using a UV–vis spectrophotometer. The reliability and stability of the composite cells with E48/S811 and azobenzene derivatives were studied. The photoisomerization of the chiral polymer film was investigated by using SEM and AFM analyzers. It was found that the UV irradiation of a laser spot caused the shrinkage of polymer film due to the photoisomerization of azobenzene segments. The contraction of the polymer film can be recovered by heat treatment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3693–3704, 2004     

UV‐Triggered Optical Response and Oxygen Scavenging Ability of a Water‐Soluble Poly(N,N‐dimethylacrylamide‐co‐2‐vinylbenzylanthraquinone) Copolymer

A vinyl‐modified anthraquinone (AQ) derivative (Vinyl‐AQ) is synthesized through a palladium‐mediated Suzuki coupling reaction between vinylphenylboronic acid and 2‐chloromethylanthraquinone and, subsequently, copolymerized with N,N‐dimethylacrylamide (DMAM) through free radical copolymerization in organic solvent. The chemical structure of the resulting water‐soluble copolymer, P(DMAM‐co‐AQ), is verified using techniques such as proton nuclear magnetic resonance, attenuated total reflection‐infrared spectroscopy, thermogravimetric analysis, and UV–vis spectroscopy. The evolution of the oxygen scavenging abilities of aqueous P(DMAM‐co‐AQ) solutions after UV irradiation is monitored as a function of UV irradiation time, concentration of AQ moieties, and pH. The copolymer is proved an effective UV‐triggered oxygen scavenger, leading to dissolved oxygen contents below 1 ppm for the optimized experimental conditions. This behavior is related with the appearance of novel chemical species with interesting optical properties, as suggested by the respective evolution of the UV–vis absorption and photoluminescence spectra after UV irradiation.     

Thermally induced microstructural changes and its influence on electrical conductivity of a polymer‐based bakelite RPC detector material: A positron lifetime study

Annealing studies have been carried out to understand the temperature induced microstructural changes in Bakelite (P‐120 NEMA LI‐1989 Grade XXX) Resistive Plate Chamber (RPC) detector material using Positron annihilation lifetime spectroscopy (PALS), Fourier transform infrared spectroscopy (FTIR), and XRD. The variation of positron lifetime parameters viz., ortho‐Positronium lifetime (τ₃) and free volume size (V_f) increases marginally above glass transition temperature T_g as a result of structural changes due to segmental mobility. The drastic increase of free volume parameters above 240°C attributed to the reduction in strength of C—H bond of the aliphatic bridges and cleavage of methylene bridges of the polymer network, which is supported by the FTIR results. The XRD results show the reduction in crystallinity and average crystallite size of Bakelite on annealing correlates well with the free volume and electrical conductivity. The temperature induced electrical conductivity and activation energy is also correlated with the positron lifetime parameters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 793‐800, 2013     

Structure and optical investigation of the effect of electron beam‐irradiation in poly‐allyl‐diglycol‐carbonate

The effect of electron beam irradiation on the structural and optical properties of Poly‐Allyl‐Diglycol‐Carbonate CR‐39 solid state nuclear track detector was investigated. Samples from CR‐39 detector were irradiated with electron beam with doses at levels between 10 and 140 kGy. The structural and optical modifications in the electron beam irradiated CR‐39 samples have been studied as a function of dose using different characterization techniques such as FTIR spectroscopy, Vickers hardness, refractive index and color difference measurements. The electron beam irradiation in the dose range 25–140 kGy led to a more compact structure of CR‐39 polymer, which resulted in an improvement in its hardness with an increase in the refractive index. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Light‐triggered reversible solubility of α‐cyclodextrin and azobenzene moiety complexes in PDMAA‐co‐PAPA via molecular recognition

Photoresponsive polymer with azobenzene pendant group (PDMAA‐co‐PAPA) was synthesized by radical polymerization of N,N‐dimethylacrylamide (DMAA) and N‐4‐phenylazophenyl acrylamide (PAPA), and the characterization of the inclusion complexes of the PDMAA‐co‐PAPA with α‐cyclodextrin (α‐CD) were performed by FTIR, GPC, ¹H NMR, 2D NOESY, and UV–vis spectroscopy. It was found that the solubility of PDMAA‐co‐PAPA and α‐CD inclusion complexes in aqueous solution showed tunable property, which could be triggered by alternating UV–vis light irradiation at a certain temperature due to the effect of molecular recognition of α‐CD with azobenzene moiety in the polymer. After UV irradiation, the lower critical solution temperature (LCST) of the polymer aqueous solution increased slightly without α‐CD while the LCST decreased sharply at presence of α‐CD. Furthermore, UV spectroscopy showed that the photoisomerization of the polymer solution went on rapidly and reversibly, and 2D NOESY data suggested that the inclusion complexation of α‐CD with trans azobenzene moiety and the decomplexation with cis azobenzene resulted in reversible solubility behavior when objected to UV and Vis light irradiation alternately. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of UV‐irradiation and molten medium on the mechanical and thermal properties of polystyrene–polycarbonate blends

Polymer materials with improved properties can be obtained through polymer blends. As a polymer mixture is generally immiscible and incompatible, it is necessary to develop new methods to improve the interfacial adhesion. The aim of this work is to find formulations and associated processes to upgrade engineering polystyrene (PS) and polycarbonate (PC) polymer blends with the objective of using the best “process‐formulation” couple. In this study, blends of PS/PC were prepared in molten medium using reactive extrusion after UV‐irradiation. The effects of UV‐irradiation on some properties of blends under molten medium were investigated by differential scanning calorimetry (DSC), fourier transform infrared (FTIR), and thermogravimetric analysis (TGA). The data showed that the presence of polycarbonate in the blend increased the tensile strength and elongation at break with respect to pure PS. The mechanical properties of the blends were improved after irradiation. All irradiated blends are thermally more stable than those nonirradiated. Chemical changes can be clearly seen in FTIR spectra through two bands assigned to C?O and OH groups. The mutual influence between the PS/PC polymer blends compositions during UV‐irradiation was studied. PS and PC have different photo‐mechanisms due to the larger UV absorption of polystyrene and formation of more stable tertiary carbon radicals. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and properties of new conducting polyaniline/copper sulfide nanocomposites

This article reports the facile synthesis of copper sulfide (CuS)/polyaniline (PANI) nanocomposites by in situ polymerization. The composites were characterized by scanning electron microscopy (SEM), UV–visible and Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). SEM analysis showed that the metal sulfide nanoparticles were uniformly dispersed in the polymer matrix. The characteristic peaks in FTIR and UV–vis spectra of PANI were found to be shifted to higher wave numbers in PANI/CuS composite, which is attributed to the interaction of CuS nanoparticles with PANI chain. XRD pattern revealed the structurally ordered arrangement of polymer composite and this regularity increases with increase in concentration of nanoparticles. Glass transition temperature of the nanocomposite increased with increase in the concentration of nanoparticles and it indicated the ordered arrangement of the polymer composite than PANI. TGA studies indicated excellent thermal stability of polymer nanocomposite. The electrical properties of nanocomposites were studied from direct current and alternating current resistivity measurement. Conductivity, dielectric constant, and dissipation factor of the nanocomposite were significantly increased with the increase in CuS content in the nanocomposite. The enhancement of these properties suggests that the proposed PANI/CuS nanocomposites can be used as multifunctional materials for nanoelectronic devices. POLYM. ENG. SCI., 54:438–445, 2014. © 2013 Society of Plastics Engineers     

Synthesis and optical properties of ZnSe micro-grasses and microspheres grown on graphene oxide sheets by the hydrothermal method

Zinc selenide (ZnSe) micro-grasses and microspheres have been successfully grown on graphene oxide sheets by the hydrothermal method. The morphologies, structures, chemical compositions and optical properties of the as-synthesized graphene oxide (GO)/ZnSe microstructures have been characterized by X-ray power diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), ultraviolet-visible (UV–vis) absorption spectroscopy and photoluminescence (PL) spectroscopy. By adjusting the concentration of NaOH and EDTA, needle-like, coral grass-like, orchid-like, and spherical ZnSe microstructures have been synthesized.