An analysis of the changes in the structure and tensile properties of polytetrafluoroethylene films under vacuum ultraviolet irradiation

The effect of 5–200 nm of vacuum ultraviolet (VUV) irradiation on the structure and tensile properties of polytetrafluoroethylene (PTFE) films was investigated. The change in structure before and after VUV irradiation was evaluated with differential scanning calorimetry (DSC) and electron spin resonance (ESR) analysis. DSC analysis results showed that the melting point, melting enthalpy, and crystallization enthalpy increased and the maximum crystallization temperature decreased a little with increasing VUV dose. It was deduced from the DSC data that the molecular weight of the PTFE films decreased and the destruction of the crystal structure took place under VUV irradiation. The ESR results showed that the radicals formed under VUV irradiation were chain‐end radicals and peroxy radicals, which may have been formed due to the scission of carbon‐to‐carbon bonds. The tensile fracture strength and elongation decreased with increasing VUV irradiation dose. Under the same irradiation dose, the tensile properties were more sensitive to the lower VUV intensity. The decrease in the molecular weight and the destruction of crystal structure might have been the major reasons for the deterioration of the tensile properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1494–1497, 2004     

Melt flow indexer evidence of high‐temperature transitions in molten high‐density polyethylenes

A melt flow indexer (MFI) was used to investigate high‐temperature transitions in melts of high‐density polyethylene (HDPE). The MFI data were obtained in the range 190–230°C. These transitions were found in the MFI at about 210 and 225°C and reproduced in a Haake melt blender. Polystyrene was used in the blender experiment to demonstrate typical amorphous behavior. For HDPE melts, the MFI–temperature behavior and the torque–temperature data of the blender were found to be alternative images of the same anomalous temperature dependency in the range 210–225°C. Also, the Haake melt blender was able to reproduce the 150°C transition observed by Kolnaar and Keller in the extrusion of HDPE. Regardless of the simplicity of the MFI device, results are in agreement with our previous DSC findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1309–1313, 2004     

Presence of vacuoles in natural rubber–Cloisite 15A nanocomposites

We studied natural rubber (NR) filled with frequently used organoclay Cloisite 15A using transmission electron microscopy (TEM), cryoporosimetry, and electron spin resonance (ESR) spectroscopy. Quantitative analysis of the TEM micrographs showed a high level of dispersion without the formation of a rigid filler network. The presence of vacuoles was established on the surface of Cloisite 15A; this indicated weak filler–matrix interactions. The mechanism of reinforcement is, therefore, discussed. The volume of vacuoles was found to be proportional to the crosslinking density; this was confirmed with ESR spin‐probe method. The shape of the ESR spectra was highly influenced by the presence of vacuoles. In the NR–Cloisite 10A nanocomposites, vacuoles were absent. The strong interactions implied by this result were confirmed by ESR measurements and are discussed further. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44776.     

Thermal behavior of acrylonitrile carboxylic acid copolymers

Polyacrylonitrile (PAN) and copolymer of acrylonitrile–vinyl acids prepared by solution polymerization technique have been characterized by Differential Scanning Calorimetry (DSC) (under dynamic as well as isothermal conditions), themograviemetric analysis (TGA), and on‐line DSC‐FTIR spectroscopy. The DSC of copolymers was carried out at 5°C/min in nitrogen and air. In nitrogen atmosphere the DSC exotherm show a very sharp peak, whereas, in air atmosphere DSC exotherm is broad, and starts at a much lower temperature compared to what is observed in nitrogen atmosphere. The initiation temperature of PAN homopolymer is higher than that for the copolymers. For instance, the initiation temperature of PAN in air is 244°C, whereas, the onset of exothermic reaction is in the range of 172 to 218°C for acrylonitrile–vinyl acid copolymers. As the vinyl acid content increases the ΔH value reduces. The ΔH value of PAN in air was 7025 J/g, whereas, for P(AN‐AA) with 5.51 mol % of acid it was 3798 J/g. As the content of acrylic acid comonomer is increased to 17.51 mol % the value of ΔH decreases further to 1636 J/g. The same trend was observed with MAA and IA as well. DSC‐FTIR studies depict various chemical changes taking place during heat treatment of these copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 685–698, 2003     

Kinetic study of radical polymerization. II. Solid‐state bulk polymerization of sodium methacrylate by differential scanning calorimetry

The solid‐state radical polymerization of sodium methacrylate was investigated. It was initiated by azobisisobutyronitrile, which was used as a radical initiator. Differential scanning calorimetry (DSC) was used to observe the endothermic and exothermic transitions during the polymerization reaction. Structural studies were performed with the DSC thermograms and Fourier transform infrared and ultraviolet–visible spectra, and all of the results confirmed the progress of the reaction. The obtained data revealed that the polymerization reaction proceeded completely with a 100% conversion. ΔH of this reaction was calculated with various amounts of the initiator, and the peak temperatures were determined at different heating rates. The activation energy (19.7 kcal mol^?1) was also obtained by the Kissinger method for this type of solid polymerization reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1648–1654, 2003     

Analysis of the isothermal crystallization of isotactic polypropylene nucleated with sorbitol derivatives

The isothermal crystallization kinetics of isotactic polypropylene (iPP) and iPP nucleated with the sorbitol derivatives 1,3:2,4‐bis(4‐methyldibenzylidene)sorbitol and 1,3:2,4‐bis(3,4‐dimethylbenzylidene)sorbitol was studied, along with the subsequent melting behavior, as a function of the nucleating agent concentration. The influence of the agents on the crystallization rate, crystallization temperature, and crystallization range was examined. The isothermal crystallization temperature increased, along with the crystallization rate, with increasing nucleating agent concentration. The maximum effect of the additives occurred at concentrations of 0.3% or greater. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2261–2274, 2003     

Compatibility of polysaccharide/maleic copolymer blends. IV. Thermal behavior of hydroxypropyl cellulose‐containing blends

The compatibility of the hydroxypropyl cellulose (HPC) with maleic acid–vinyl acetate copolymer in the solid state was studied by thermogravimetry, thermo‐optical analysis, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and optical microscopy. It was established that physical interactions are prevalent in blends with a high content of HPC, whereas chemical interactions predominate in blends with a medium and low content of HPC. By increasing the temperature, the thermochemical reactions are favored. Thermal properties are dependent on the mixing ratio of the components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2585–2597, 2003     

Dynamic mechanical properties of sandwich‐structured epoxy beam composites containing poly(ethyleneterephthalate)/poly(ethyleneglycol) copolymer with shape memory effect

To make smart vibration‐controlling composite laminate, a few poly(ethylene terephthalate) (PET) and poly(ethylene glycol) (PEG) copolymers with shape memory ability were prepared. After selecting the best composition of PET–PEG copolymer in mechanical properties, a crosslinking agent such as glycerine, sorbitol, or maleic anhydride (MA) was included for crosslinked copolymer, followed by analysis of its effect on mechanical, shape memory, and damping properties. The highest shape recovery was observed for copolymer with 2.5 mol % of glycerine, and the best damping effect indicating vibration control ability was from copolymer with 2.5 mol % of sorbitol. With the optimum copolymers in hand, sandwich‐structured epoxy beam composites fabricated from an epoxy beam laminate and crosslinked PET–PEG copolymer showed that impact strength increased from 1.9 to 3.7 times depending on the type of copolymer, and damping effect also increased as much as 23 times for the best case compared to epoxy laminate beam alone. The resultant sandwich‐structured epoxy beam composite can be utilized as structural composite material with vibration control ability, and its glass transition temperature can be controlled by adjustment of PET, PEG, or crosslinking agent composition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3141–3149, 2003     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (T_g) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three T_g values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003     

Synthesis and characterization of polyurethane–chitosan interpenetrating polymer networks

A polyurethane–chitosan (PU–CH) coating was synthesized from castor-oil-based PU prepolymer and highly deacetylated and depolymerized chitosan. The films cast with the coating were used for the characterization. X-ray photoelectron spectroscopy, a surface-sensitive technique, indicated the chemical bonding between the chitosan and PU prepolymer as well as the enrichment of chitosan on the surface of the film PU–CH. Electron spin resonance (ESR) spectroscopy using the nitroxyl radical 4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl (4-hydroxy-TEMPO) as a reporter group was used to study the chain mobility in the film PU–CH. It was observed that T_50G of the probe and the first glass transition temperature (T_g1) of the film PU–CH were 10 and 18°C higher than those in the PU film, respectively, and the activation energy (27.0 kJ mol⁻¹) of tumbling for the probe covalently bonded with PU–CH was 12.8 kJ mol⁻¹ higher than that of the probe with the film PU. It suggests that the molecular motion in the PU–CH was restricted by grafted and crosslinked interpenetrating polymer networks (IPNs). The results of the differential thermal analysis and thermogravimetric analysis proved that the thermostability of the film PU–CH was significantly higher than that of the film PU, and the T_g1 value is in good agreement with that calculated from ESR. It could be concluded that the IPNs resulted from the chitosan grafting and crosslinking with PU exist in the film PU–CH. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1321–1329, 1998     

Enhancement of mechanical properties and interfacial adhesion of PP/EPDM/flax fiber composites using maleic anhydride as a compatibilizer

In order to improve the compatibility between natural fibers and polypropylene (PP) and polypropylene‐ethylene propylene diene terpolymer (PP‐EPDM) blends, the functionalization of both matrices with maleic anhydride (MA) is investigated in this study. The morphological observations carried out by scanning electron microscopy show that the incorporation of small amounts of functionalized polymer considerably improves the adhesion at the fiber‐matrix interface. In these cases, the fibers are perfectly embedded in the matrix in relation to the composites prepared with the pure homopolymers, and a significant increase in the composite strength is also observed, particularly, after the incorporation of both modified polymers (MAPP and MAEPDM). Thus, it is possible to correlate better interfacial adhesion with the improvement of mechanical properties. It is assumed that the functionalization of the matrix reduces interfacial stress concentrations and may prevent fiber‐fiber interactions, which are responsible for premature composite failure. The crystallization kinetics of PP were also analyzed by differential scanning calorimetry (DSC). It was observed that both flax fiber and rubber behave as effective nucleant agents, accelerating PP crystallization. Moreover, these results are particularly relevant when the grafted matrices are added to the composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2170–2178, 2003     

Stimuli‐responsive properties of aminophenylboronic acid‐carrying thermosensitive copolymers

Thermosensitive copolymers of N‐isopropylacrylamide (NIPA) and N‐acryloxysuccinimide (NASI) were obtained by solution polymerization using azobisisobutyronitrile as the initiator in a tetrahydrofuran–toluene mixture at 65 °C. A boronic acid‐carrying ligand, m‐aminophenylboronic acid (APBA) was covalently attached to the thermosensitive copolymer via the reaction between amino and succinimide groups. APBA‐coupled thermosensitive copolymer exhibited both temperature and pH sensitivity. Thermally reversible phase transitions were observed both in the acidic and alkaline pH region for the APBA‐modified copolymers obtained with different NASI feed concentrations. In our study, ribonucleic acid (RNA) was selected as a biomolecule having reactive groups which could potentially interact with the boronic acid functionality. The response of boronic acid‐carrying thermosensitive copolymer against RNA was investigated in aqueous media in the pH range 4–9. In the acidic pH region, an increase was observed in the lower critical solution temperature (LCST) of the APBA‐coupled thermosensitive copolymer with increasing RNA concentration. However, LCST decreased with increasing RNA concentration at both neutral and alkaline pH values. The LCST of the APBA‐attached copolymer varied linearly with the RNA concentration at pH of 3, 4 and 7. © 2003 Society of Chemical Industry     

Studies on the critical phase‐transition behavior of cholesteric N‐phthaloyl chitosan/dimethyl sulfoxide solutions by five techniques

A selectively side‐modified chitosan derivative, N‐phthaloyl chitosan (PhthCs), was prepared. Five techniques, including circular dichroism (CD) spectropolarimetry, ultraviolet–visible (UV–vis) spectroscopy, small‐angle light scattering (SALS), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), were simultaneously applied to investigate the order–disorder phase transition for the lyotropic PhthCs/dimethyl sulfoxide system. POM observations suggested that the critical concentration was 48 wt %, which agreed well with the DSC measurements. A four‐leaf SALS picture was recorded in biphasic solutions. The four‐leaf type became a circular symmetric scattering picture with a further increase in the concentration. A sharp peak at 330 nm was recorded in dilute isotropic solutions with CD measurements. The sharp peak turned into a broad tailed peak from 330 to 800 nm after the phase transition occurred. The sharp peak was induced by a chromophore (phthoyl group). The broad peak was attributed to the formation of short‐range‐ordered organization in the concentrated solutions. In UV–vis studies, when the system varied from isotropic to anisotropic, the absorption band turned into platform. These five techniques were proven to be feasible methods for measuring the phase transition of cholesteric liquid crystals. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 583–586, 2003     

Investigation of liquid diffusion into contact lenses using an electron spin resonance technique

In this study, electron spin resonance (ESR) spectroscopy was used for the first time to investigate liquid diffusion into contact lenses. As contact lenses are not paramagnetic substances, they were labeled with nitroxide spin probes to get an ESR spectrum. Thus, it gives a solid spin‐labeled ESR spectrum. The shape and intensity of the ESR signals depend on the environment of these spin probes. The spin probe environment began to change from solid to liquid if liquid were dropped into the system. Consequently the ESR spectra began to change with time, too. By following these changes, three distinct steps were found. Their diffusion coefficients were determined to be 6.38 × 10^?8 cm²/s for the first step (rapid decay region) and 0.37 × 10^?8 cm²/s for the second step (slow decay region), and 2.50 × 10^?8 cm²/s for the third and last step (desorption region). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2942–2946, 2006     

Application of magnetic resonance techniques in investigation of hydrocarbons interaction with composite polymers

Composite polymers such as high impact poly stirene (HIPS) or acrylonitrile–butadiene–styrene (ABS) are widely used in manufacturing industry. In special applications, such as refrigerator liners, a good resistance to fluids aggression is required. In this study we have applied NMR and ESR techniques to investigate the effect of diffusion of fluids (light hydrocarbons) used as blowing agents for polyurethanes (thermal insulators) inside selected HIPS materials. The application of NMR relaxation analysis on materials exposed to deuterated hydrocarbons (C₆D₁₂) allowed selective observation of rubber phase modification. Both longitudinal (T₁) and transversal (T₂) relaxation provided information on polymer chain dynamics effects, determined by solvent interactions. In fact, a consistent increase in relaxation times of polybutadiene rubber phase after solvent exposition was observed. Similar results were obtained by using hexachlorobutadiene as solvent. Another confirmation was also obtained by spin‐probe ESR technique. This technique could give useful insight into the molecular mobility of the two phases of HIPS. This experimental investigation provided a clear demonstration of consistent solvent penetration inside the rubbery phase of such composite polymers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2810–2817, 2006     

Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Stress‐induced crystallization of biaxially oriented polypropylene

The hot stretching of thick, extruded sheets at high temperatures is a very important process in the production of finished biaxially oriented polypropylene (BOPP) films with special inner structures. Through a simulation of hot stretching in the machine direction (MD) of the processing of BOPP films, it was found that at high temperatures, the stretching ratio greatly influenced the obtained crystalline structure, as observed by differential scanning calorimetry (DSC). Also, in MD hot stretching, the crystallinity increased by an average of 20%. Wide‐angle X‐ray diffraction patterns of extruded sheet samples with and without stretching confirmed the structural changes shown by DSC, and the results proved that β‐crystal modification did not occur during the MD hot‐stretching process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 686–690, 2003     

Synthesis and characterization of poly(dimethylsiloxane)–polythiophene composites

The synthesis was performed by the electropolymerization of thiophene on a poly(dimethylsiloxane) (PDMS)‐coated platinum electrode at 2.2 V with tetrabutylammoniumtetrafloroborate (TBAFB) as a supporting electrolyte and with acetonitrile as a solvent. The characterization of the PDMS–polythiophene (Pth) composites was carried out with cyclic voltammetry, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis, and conductivity measurements. The observed conductivities of the PDMS composites were 2.2–5.2 S/cm. The conductivity of Pth did not change appreciably with the addition of up to 30% insulating PDMS, but its processability improved. FTIR, SEM, and DSC studies showed the existence of a strong interaction, rather than physical adhesion, between PDMS and Pth. Highly flexible and foldable PDMS–Pth composites were obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2113–2119, 2003     

Polymaleamide–polymaleimide networks

Polymaleamide–polymaleimide networks were obtained as films by the thermal treatment of mixtures with different ratios of an aliphatic–aromatic polymaleamide (PMA) and 4,4′‐bis(maleimidodiphenylmethane) (BMI), in N‐methyl‐2‐pyrolidinone (NMP) as a solvent. The polymaleamides were synthesized by ring‐opening polyaddition of 1,6‐hexamethylene–bisisomaleimide with 4,4′‐diaminodiphenylmethane in NMP at room temperature. The networks are infusible and insoluble in organic solvents; therefore, they were studied by solid‐state techniques such as IR, DSC, thermooptical analysis (TOA), TG/DTG analysis, and TEM. Thermal treatment of pure PMA and BMI occurs with the formation of crosslinked structures as proved by IR spectra. DSC and TOA curves show the appearance of chemical interactions between PMA and BMI in cured films and the formation of ordered morphologies, especially when BMI is the major component. TG/DTG and TEM results supported these observations. The PMA–polymaleimide network films present electrical insulator properties superior to individual polyamides or polyimides. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 779–788, 2004