Electron microscopy of macroporous cellulose (acetate–co–butyrate)–polycarbonate semi–interpenetrating networks

Summary Summary Semi–interpenetrating polymer networks, s–IPNs, were prepared from cellulose acetate–co–butyrate (CAB), still containing 46% OH groups, and diethylene glycol bis allylcarbonate (CR39) which was crosslinked by free–radical polymerization initiated by benzoyl peroxide. Microstructure of s–IPNs (CAB/CR39) of relative weight proportions between 0.2/1 and 0.411 was examined by electron microscopy (TEM and SEM). Spheroidal compact objects of several µm diameter are randomly distributed within a microporous phase in which the pore connectivity was shown by density measurements. Such a microstructure is consistent with the formation of CAB polymer dispersed phase in a poly (CR39) network continuous phase.     

Determination of the transition phenomena of poly(α-n-alkyl) methacrylates adsorbed on silica by inverse gas chromatography (IGC)

Inverse gas chromatography (IGC) at infinite dilution is a powerful technique to characterise the superficial and interfacial properties of solid substrates as oxides, polymers or polymers adsorbed on oxides and to determine the transition phenomena of polymers. This technique was applied in earlier studies in order to determine the change, as related to temperature, of the properties and the second order transitions of some polymers adsorbed on oxides, and particularly to study the transition phenomena in PMMA and poly(α-n-propyl) methacrylate (P3) adsorbed on silica or in their bulk phases. In this paper, the superficial properties and glass transitions of poly(α-n-pentyl) methacrylate (P5) and poly(α-n-octyl) methacrylate (P8) were studied when adsorbed on silica or in their bulk phases. The study of the evolution of RTlnVn, as a function of 1/T for different n-alkanes adsorbed on poly(α-n-alkyl) methacrylates (Pn), proved that IGC technique allowed a fairly accurate determination of their transition temperature (Tg). Moreover, the glass transition temperature Tg was observed to vary from 110 °C for PMMA (P1) to 10 °C for poly(α-n-octyl) methacrylate. Results obtained in this study proved an important shift in the value of Tg, due to the adsorption of various Pn on silica and the more spread chains of the adsorbed polymers. A reduction in Tg value was observed when the length of the side chain increases that leads to an internal plastification effect in poly(α-n-alkyl)methacrylates.     

Modeling of interdiffusion in poly(vinyl acetate)–poly(methyl methacrylate)–toluene multicomponent systems

Work on interdiffusion has been mainly carried out in binary systems in the past, and this work has focused on polymer–solvent (S) systems and polymer blends. To understand and predict the interdiffusion of two solids in the presence of one S, we present a new mathematical model based on the Onsager approach. Within our model, interdiffusion kinetics are described with a modification of the reptation model for long polymer chains, and the chemical potential gradient is used as the driving force behind mass transfer. The chemical potential is calculated with a Flory–Huggins approach. The model was validated with 29 Raman spectroscopy experiments in poly(vinyl acetate)–poly(methyl methacrylate)–toluene systems at 20 °C. Monomer mobilities (L _i,0s) were determined for both polymers to show the independence of L _i,0 from the chain length. The L _i,0s were found to be strongly dependent on the S content. With the knowledge of phase equilibria and L _i,0s, interdiffusion in the ternary polymer–polymer–S system could be predicted by the introduced model. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47092.     

Structural characterization of poly(ε-caprolactone)-grafted cellulose acetate and butyrate by solid-state C NMR, dynamic mechanical, and dielectric relaxation analyses

Investigations were made into the molecular dynamics and intercomponent mixing state in solid films of two series of cellulosic graft copolymers, cellulose acetate-g-poly(ε-caprolactone) (CA-g-PCL) and cellulose butyrate-g-PCL (CB-g-PCL), both series being prepared over a wide range of compositions with CAs or CBs of acyl DS ≈ 2.1, 2.5, and 2.95. It was shown by T_1ρ^H measurements in solid-state ¹³C NMR spectroscopy that all the copolymer samples, except ones using CA of DS = 2.98, formed an amorphous monophase in which the trunk and graft components were mixed homogeneously at least in a scale of a few nanometers. However, those copolymer samples gave, more or less, a response of dynamic heterogeneity, when examined under mechanical oscillation. Through dielectric relaxation measurements, a clear comparison was made between the CA-g-PCL and CB-g-PCL series, regarding the cooperativeness in segmental motions of the trunk and graft chains, directly associated with the extent of the dynamic heterogeneity. The cooperativeness was generally higher in the CB-based copolymer series, probably due to working of the butyryl substituent as an internal compatibilizer.     

Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation

Blend PES/CA hydrophilic membranes were prepared via a phase-inversion process for oil–water separation. PEG-400 was introduced into the polymer solution in order to enhance phase-inversion and produce high permeability membranes. A gas permeation test was conducted to estimate mean pore size and surface porosity of the membranes. The membranes were characterized in terms of morphology, overall porosity, water contact angle, water flux and hydraulic resistance. A cross-flow separation system was used to evaluate oil–water separation performance of the membranes. From FESEM examination, the prepared PES/CA membrane presented thinner outer skin layer, higher surface porosity with larger pore sizes. The outer surface water contact angle of the prepared membrane significantly decreased when CA was added into the polymer solution. The higher water flux of the PES/CA membrane was related to the higher hydrophilicity and larger pore sizes of the membrane. From oil–water separation test, the PES/CA membrane showed stable oil rejection of 88 % and water flux of 27 l/m² s after 150 min of the operation. In conclusion, by controlling fabrication parameters a developed membrane structure with high hydrophilicity, high surface porosity and low resistance can be achieved to improve oil rejection and water productivity.     

Selective surface modification of ethylene-vinyl acetate and ethylene polymer blend by UV–ozone treatment

Ethylene-vinyl acetate (EVA) copolymers intended for sport sole manufacturing may contain noticeable amounts of polyethylene (LDPE) for improving abrasion resistance and decrease cost; however, this blend (EVA–PE) had low polarity and showed poor adhesion. In this study an effective environmentally friendly and fast surface treatment based on UV–ozone has been used to increase the wettability, polarity and roughness of EVA–PE material. Both the length of the UV–ozone treatment and the distance between the material surface and the UV-radiation source were tested. The UV–ozone treated EVA–PE material was characterized by ATR-IR spectroscopy using Ge prism, water contact angle measurements, X-Ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Adhesion properties were obtained from T peel tests of as-received and UV–ozone treated EVA–PE/polyurethane adhesive/leather joints.The more extended length of treatment and the shorter UV source–substrate distance increased the wettability of the EVA–PE material. Oxidation of the EVA–PE surface was produced by UV–ozone treatment creating new carbonyl groups mainly, and the amounts of hydroxyl and carboxylic groups were increased. The UV–ozone treatment produced ablation and etching of the EVA–PE material surface, mainly in the vinyl acetate, creating a particular roughness consisting on ruffles with deep crevices; this topography was also produced by heating produced during UV–ozone treatment. For low length of UV treatment or high UV source–material distance, the modifications of the EVA–PE material were mainly produced in the ethylene causing the selective removal of vinyl acetate, whereas more aggressive conditions produced strong oxidation in the EVA–PE material. Finally, adhesive strength was noticeably increased in the UV–ozone treated EVA–PE/polyurethane adhesive joints, and a cohesive failure in the leather was obtained.     

Review on transesterification in polycarbonate–poly(butylene terephthalate) blend

Various polycarbonate - poly(butylene terephthalate) polyester (PC-PBT) blend prepared by reactive melt blending primarily in extruder with range of temperature and time are discussed in this review article. In the melt blended PC-PBT blend system, transesterification plays a major role in formation of PC-PBT blend. Transesterification reactions between these two polymers have been analyzed by proper polymer sample, end-capped or having reactive chain end group. The kinetics of mechanism is a function of temperature and PC-PBT ratio. Trace catalyst residue present in PBT catalyzes the transesterification reaction. As the extent of transesterification is increased, it forms various composition of copolymer. Inhibition in the transesterification reaction of PC-PBT blend has been observed when different type of alkyl, aryl, and alkyl-aryl group of phosphite are introduced into it, otherwise there has been collateral change in the morphology, thermal, and mechanical property of blend. Therefore, this PC-PBT blend has been an interesting topic of research in academia and industries.     

Morphological characteristics and thermal,rheological, and mechanical properties of cellulose nanocrystals-containing biodegradable poly(lactic acid)/poly(ε-caprolactone) blend composites

This work investigates the effect of cellulose nanocrystal (CN) loading on the properties of polylactide / poly(ε-caprolactone) (PLA/PCL) (70/30) blend processed in a twin-screw extruder as a potential material that can be utilized in various applications where biodegradation is highly desired. The morphological analysis revealed a reduction in droplet size of dispersed PCL phase upon addition of CN at low concentrations (1 and 2 wt %) with maximum reduction at 2 wt % which led to maximum improvement in mechanical properties. The reinforcing effect of CN in increasing the DMA storage modulus of the prepared systems was noticed when CN concentration was increased. Further, CN enhanced the crystallization of PCL, whereas the cold crystallization of PLA remained the same with CN addition. Both melt strength and viscosity of PLA improved with the incorporation of PCL and CN. In general, a green composite material with improved properties was successfully prepared using an environmentally friendly filler material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48665.     

In vitro degradation of poly(l-lactide)/poly(ε-caprolactone) blend reinforced with MWCNTs

The physical and mechanical properties of poly(l-lactide)/poly(??-caprolactone) (PLLA/PCL) blends reinforced with multiwalled carbon nanotubes (MWCNTs) before and after in vitro degradation were investigated. Because of brittleness, PLLA needs to be plasticized by PCL as a soft polymer. The MWCNTs are used to balance the stiffness and the flexibility of PLLA/PCL blends. The results showed that with incremental increase in concentration of MWCNTs in composites, the agglomerate points of MWCNTs were increased. The physical and mechanical properties of prepared PLLA/PCL blends and MWCNT/PLLA/PCL nanocomposites were characterized. The X-ray diffraction analysis of the prepared blends and composites showed that MWCNTs, as heterogeneous nucleation points, increased the lamella size and therefore the crystallinity of PLLA/PCL. The mechanical strength of blends was decreased with incremental increase in PCL weight ratio. The mechanical behavior of composites showed large strain after yielding and high elastic strain characteristics. The tensile tests results showed that the tensile modulus and tensile strength are significantly increased with increasing the concentration of MWCNTs in composites, while, the elongation-at-break was decreased. The in vitro degradation rate of polymer blends in phosphate buffer solution (PBS) increased with higher weight ratio of PCL in the blend. The in vitro degradation rate of nanocomposites in PBS increased about 65% when the concentration of MWCNTs increased up to 3% (by weight). The results showed that the degradation kinetics of nanocomposites for scaffolds can be engineered by varying the contents of MWCNTs.     

Compatibilizing capability of poly(β-hydroxybutyrate-,co-ε-caprolactone) in the blend of poly(β-hydroxybutyrate) and poly(ε-caprolactone)

In order to increase the miscibility in the blend of poly(β-hydroxybutyrate) [PHB] and poly(ε-caprolactone) [PCL], PHB/PCL copolyesters were used as compatibilizers. These PHB/PCL copolyesters were synthesized by transesterification in solution phase. The melting point [T_m] depression, which was not observed in PHB/PCL blend without compatibilizer, was observed when PHB/PCL copolyesters as compatibilizers were added to the PHB/PCL blend system. As the amount of compatibilizer added to the blend increased, the crystallization temperature [T_c] of PCL in the blend increased and T_c of PHB in the blend decreased. The difference in T_c between PHB and PCL was gradually reduced. When the sequence length of PHB block and PCL block in the PHB/PCL copolyester increased, the miscibility of the blend increased. This is evidenced by the depression in the T_m of PHB and PCL in the blend and by the decrease in the difference of T_c between PHB and PCL. From the polarizing optical micrographs, the phase separation in PHB/PCL blend was observed. However, in the presence of PHB/PCL copolyester, the spherulite of PHB grows in equilibrium with one phase melt. Received: 27 July 1998/Revised version: 12 October 1998/Accepted: 4 November 1998     

Effects of process parameters on the physical properties of poly (urea–formaldehyde) microcapsules prepared by a one-step method

The physical properties of microcapsules are strongly influenced by the synthetic conditions used for their preparation. To prepare microcapsules possessing a smooth surface morphology, high mechanical strength, and reduced permeability of the core material, in situ polymerization in an oil-in-water emulsion was performed using poly (urea–formaldehyde) and tetrachloroethylene as the shell and core materials, respectively. The influence of the synthetic conditions, including the initial pH value, concentration of wall material, concentration of NaCl, and heating rate, on the properties of the resulting microcapsules was investigated systematically by an orthogonal factorial design. The physical properties of the microcapsules were characterized using scanning electron microscopy and optical-photographic microscopy. The results showed that the concentration of shell material has a substantial effect on the mechanical strength of the microcapsules. Additionally, a slow heating rate and high initial pH value enhance the preparation of well-defined spherical microcapsules having excellent barrier properties. Finally, a moderate concentration of sodium chloride can remarkably improve the compactness of the capsule wall. The optimum conditions, determined on the basis of utilization of wall material, are as follows: initial pH value: 3.5; concentration of shell material: 3.6 × 10^?2 g/mL; heating rate: 0.5 °C/min; and concentration of sodium chloride: 5.0 × 10^?2 g/mL.     

Surface texture and barrier performance of poly(lactic acid)–cellulose nanocrystal extruded-cast films

In this study, we assessed the influence of cellulose nanocrystal (CNC) addition level (0.5–2 wt %) on the surface texture, thickness, and barrier properties of poly(lactic acid) (PLA) extruded-cast films. Regardless of the CNC content, the addition of CNC increased the surface average roughness and maximum roughness of the PLA films in both the machine and cross-machine directions because of the presence of CNC agglomerates. The increased roughness resulted in films with uneven thicknesses; this affected their accurate measurements with a conventional micrometer. Rather, accurate thickness measurements were obtained through the density method, a more appropriate thickness measurement method for films with rough surfaces. The permeability values were negatively correlated with the increased crystallinity. Both the water vapor permeability and oxygen permeability (OP) values decreased significantly by approximately 26–45 and 25–50%, respectively, as the CNC content increased from 0.5 to 2 wt % because of the tortuosity effect. The OP values of the neat PLA and composite films remained insensitive to changes in the relative humidity (from 0 to 75%) when they were tested at 23 °C. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47594.     

Entrap-immobilization of invertase on composite gel fiber of cellulose acetate and zirconium alkoxide by sol–gel process

We prepared a composite gel fiber by the gel formation of cellulose acetate and zirconium tetra-n-butoxide. Gel fiber is stable in common solvents, phosphate solution, and electrolyte solution. Invertase was entrap-immobilized on the gel fiber. The immobilization was easily performed under the mild conditions. The apparent Michaelis constant (K_m) and maximum reaction velocity (V_max) were estimated from Eadie–Hofstee plot for immobilized invertase. The K_m of immobilized invertase was larger than that of native invertase, while the opposite tendency was observed for the V_max. The activity for the immobilized invertase became higher with increasing fiber diameter. It indicates that the hydrolysis of sucrose occurs in the neighborhood of the fiber surface. The thermal stability of the immobilized invertase was higher than those of its native counterpart. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2084–2088, 2001     

Influence of solubility parameter difference between monomer and porogen on structures of poly (acrylonitrile–styrene-divinylbenzene) resins

In this work, the acrylonitrile (AN)-styrene (St)-divinylbenzene (DVB) resin was synthesized via suspension polymerization in the presence of inert porogens as diluent. The relationship of the solubility parameter (SP) of the materials and the porous properties of the resin was investigated. These porous spherical resin particles (0.25–0.84 mm) can be used as precursors of amidoxime resin which has a high metal ion chelating efficiency. The results showed that the porous properties (surface area and mean pore width) of the resin changed with variation in the compatibility between monomers and porogens. According to the the BET theory to N₂ sorption and scanning electron microscopy (SEM), the specific surface area of the obtained beads was strongly dependent on the compatibility of the components of the system and achieved values from 3.3 to 66.8 m²/g. The surface area of the terpolymer beads was found to rise with a decrease in the content of acrylonitrile or an increase in the SP of the porogens. However, the variation of the pore size was just the opposite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46979.     

Mechanical properties of poly(ε-caprolactone) composites with electrospun cellulose nanofibers surface modified by 3-aminopropyltriethoxysilane

To enhance the reinforcement effects of regenerated cellulose nanofibers (RC-NF) in poly(ε-caprolactone) (PCL), we synthesized RC-NF-3-aminopropyltriethoxysilane (APS), the surface-modified RC-NF by APS. The RC-NF were fabricated by the saponification of electrospun cellulose–acetate nanofibers. The surface modification by APS was confirmed by the X-ray photoelectron spectroscopy (XPS). To enhance the mechanical property of PCL, the RC-NF and the RC-NF-APS were separately compounded into PCL by compression molding. It was found that, when the fiber concentration of RC-NF-APS was 17 wt %, the Young's modulus at room temperature increased from 698.0 to 744.7 MPa, whereas the storage modulus at 55 °C almost increased from 180 to 220 MPa. The micrographs of the fracture surface of the composites revealed that the surface modification prevented the pull-out of RC-NF from PCL. It was concluded that the mechanical properties of the composites were enhanced due to the improvement of the compatibility between RC-NF and PCL by the surface modification with APS. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48599.     

Effect of electron-beam irradiation followed by annealing on the physical properties of poly(vinyl alcohol)–chitosan blend films at different weight ratios

The aim of this study was to examine the effect of electron-beam irradiation followed by annealing on the physical properties of poly(vinyl alcohol) (PVA)–chitosan (CS) blend films. Solution-cast films containing various ratios of polymers were exposed to irradiation doses of 26, 39, and 52 kGy at room temperature and then annealed at 100 °C. The results show that at all doses, with an increase in the weight ratio of CS, the gel content of the samples decreased, and the water absorption of the samples increased. The irradiation dose ranged from 26 to 39 kGy; this led to an increased gel content and a decreased degree of swelling in the samples. However, at 52 kGy, an increase in the amount of swelling was observed. X-ray diffraction analysis and scanning electronic microscopy images of the samples revealed that the increase in the irradiation dose reduced the crystallinity and increased the surface heterogeneity, respectively. The tensile strength of the blends decreased with decreasing PVA–CS weight ratio. This property of the samples increased with dose from 26 to 39 kGy and decreased at 52 kGy. The elongation at break of the samples decreased with both an increase in the irradiation dose and a decrease in the CS content. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47820.     

Rapid synthesis of high strength cellulose–poly(vinyl alcohol) (PVA) biocompatible composite films via microwave crosslinking

The present study describes microwave (MW)-assisted rapid synthesis of biocompatible poly(vinyl alcohol) (PVA) composite films that demonstrate synergy between reinforcement and crosslinking. Bacterial cellulose (5% w/w) nanowhiskers (reinforcement) and tartaric acid 35% (w/w) (crosslinker) are incorporated in PVA to prepare crosslinked cellulose–PVA composite films. The properties of thus prepared crosslinked cellulose–PVA composite films are compared with samples crosslinked with conventional hot air oven heating (CH). Crosslinking by both of the methods reduces water absorption of PVA by around an order of magnitude and improves its thermal stability. An increase in strength from 42 (PVA) to 172 MPa and 159 MPa for MW and CH crosslinked samples, respectively is also observed. Although composites prepared using MW and CH show similar properties, MW takes only 14 min compared to 2 h in case of CH. Notably, the prepared composites demonstrate hemocompatibility and cytocompatibility, and may also be explored for biomedical applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47393.     

Synthesis and characterization of poly(ester-urethane-imide)s by Diels–Alder polyaddition

Poly(ester-urethane-imide)s were prepared by Diels–Alder polyaddition of 1,6-hexamethylene-bis(2-furanylmethylcarbamate) with various bismaleimides containing ester groups in the backbone. The Diels–Alder reaction was carried out in m-cresol, at 110°C, followed by thermal and chemical aromatization of tetrahydrophthalimide intermediates. The monomers and polymers were characterized by IR, ¹H-NMR spectroscopy and elemental analysis. Thermal properties of the polymers were investigated by differential scanning calorimetry and dynamic thermogravimetric analysis.     

Polyacrylonitrile–poly(1-vinyl pyrrolidone-co-vinyl acetate) blend based gel polymer electrolytes incorporated with sodium iodide salt for dye-sensitized solar cell applications

New gel polymer electrolytes (GPEs) were prepared via the blending of a polyacrylonitrile polymer and a poly(1-vinyl pyrrolidone-co-vinyl acetate) copolymer. The sodium iodide (NaI) salt concentration was varied for each GPE sample. From ionic conductivity (σ) studies, we observed that the sample with a 40 wt % NaI salt content (N40) showed the highest σ of 3.54 × 10⁻³ ± 0.05 S/cm at room temperature, and all of the GPE samples obeyed Arrhenius behavior. The dielectric properties of the GPE samples were also analyzed to study the electrical polarization of the materials. The developed GPE samples were also characterized with X-ray diffraction and Fourier transform infrared spectroscopy. We also then used the developed GPE samples for the fabrication of dye-sensitized solar cells by sandwiching them between a photoanode and Pt counter electrode for photovoltaic studies. The highest photovoltaic performance was achieved by N40, with an efficiency of 3.04%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47810.