Phase behavior and crystallization of a poly(ethylene oxide)/cellulose acetate butyrate blend

The phase behavior of a partially miscible blend of poly(ethylene oxide) (PEO) and cellulose acetate butyrate (CAB) and the crystalline microstructure of PEO in the blend were studied with differential scanning calorimetry (DSC), optical microscopy, and synchrotron small‐angle X‐ray scattering (SAXS) methods. PEO/CAB showed a lower critical solution temperature (LCST) of 168 °C at the critical composition of PEO of 60 wt %. All blend compositions showed a single glass‐transition temperature (T_g) when they were prepared at temperatures lower than the LCST. However, with increasing CAB content, T_g of the blend changed abruptly at 70 wt % CAB; that is, a cusp existed. Below 70 wt % CAB, the change in T_g with blend composition was predicted by the Brau–Kovacs equation, whereas this change was predicted by the Fox equation at higher CAB contents. A gradual but small depression of the melting point of PEO in the blend with an increasing amount of CAB suggested that the PEO/CAB blends exhibited a weak intermolecular interaction. From DSC and SAXS experiments, it was found that amorphous CAB was incorporated into the interlamellar region of PEO for blends with less than 20 wt % CAB, whereas it was segregated to exist in the interfibrillar region in PEO for other blends with larger amounts of CAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1673–1681, 2002     

Poly(caprolactone triol) as plasticizer agent for cellulose acetate films: influence of the preparation procedure and plasticizer content on the physico‐chemical properties

The influence of the plasticizer content and film preparation procedure on the morphology, density, thermal and mechanical properties of cellulose acetate (CA) films plasticized with poly‐(caprolactone triol) (PCL‐T), were studied. Differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), scanning electron microscopy (SEM), wide‐angle X‐ray diffraction (WAXD) and infrared spectroscopy (FT‐IR) techniques were used. The films were prepared by dry‐casting CA and CA/PCL‐T in acetone or acetone/water solutions, which produced transparent and opaque films, respectively. In contrast to the transparent films, which were dense, the opaque films presented a porous morphology. However, the presence of PCL‐T reduced the opaque film porosity, increasing, in consequence, its bulk density. The TMA results revealed that PCL‐T reduced the glass transition temperature more significantly in the transparent than in opaque films. Only the transparent CA/PCL‐T films presented a melting temperature, that reduced with higher concentrations of PCL‐T, suggesting a higher ordering (crystallinity) when the films were prepared in the absence of water, as observed from WAXD curves. The mechanical properties also showed that the transparent films were more soft and tough than the opaque films. In summary, PCL‐T was a good plasticizer agent for CA films due to the presence of hydrogen bonds between the components (FT‐IR spectra). The presence of water in the dry casting process has a significant effect mainly on film morphology and mechanical properties. Copyright © 2004 John Wiley & Sons, Ltd.     

Investigation of melamine and DOPO-derived flame retardants for the bioplastic cellulose acetate

In order to identify suitable flame retardant additives for the eco-friendly polymer cellulose acetate (CA), high-melting derivatives of the known flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were combined with the thermoplastic CA and the combustion properties were tested. CA mixtures with bis-phosphonamidates (EDA-DOPO and PIP-DOPO) showed distinct flame retardation effects and a reduction of peak heat release rates (PHRR) by up to 18%. CA mixtures with MDOP, a melamine salt of DOPA (an oxidation product of DOPO), also showed considerable effects and a reduction of PHRR by up to 27%. While producing more smoke than pure CA and CA plus melamine, owing to its aromatic component, MDOP was superior to the CA mixtures with DOPO, EDA-DOPO and PIP-DOPO in this regard. The mixture of CA with melamine gave rise to a distinctly reduced formation of toxic CO and smoke when compared with pure CA. Thus, these additives can be considered for future applications of CA-based polymers with enhanced flame protection.     

Effect of pre‐treatment of sugarcane bagasse on the cellulose solution and application for the cellulose hydrogel films

Sugarcane bagasse was used as a cellulose resource, and the transparent cellulose hydrogel films were obtained from the purified cellulose by phase inversion process without chemical cross‐linking, when the dissolved cellulose in lithium chloride/N,N‐dimethyl acetamide was transformed into the solid film. On these processes, bagasse was pre‐treated by 10 wt% sodium hydroxide in the absence and presence of bleaching of 10 vol% sodium hypochlorite (NaOCl) solution in order to obtain cellulose fibers. Here, the bleaching temperature was varied from 40 to 50°C. The effect of pre‐treatment conditions on the resultant cellulose solution and hydrogel films was investigated. It was seen that strong bleaching removed most of lignin component from the bagasse. However, viscosity and size exclusion chromatogram of the cellulose indicated that this operation decreased average molecular weight of the cellulose fibers from 2.1 × 10⁶ to 4.8 × 10⁵. These property changes of fibers also caused increase of water content and weakening of mechanical strength of the resultant hydrogels. In addition, scanning probe microscopy in wet state revealed that the porous fiber network structure in the hydrogel was greatly influenced by bleaching with NaOCl. The average pore size of fiber network was decreased from 8.1 to 5.9 nm as the NaOCl treatment was at 50°C, because of expanded fibers in the swollen hydrogel. Copyright © 2016 John Wiley & Sons, Ltd.     

<Emphasis Type="Italic">Ab initio</Emphasis> calculation of the structure of acetate cellulose membranes for reverse osmosis

The elementary unit of the monoacetate cellulose membrane in lithium, sodium, and potassium chloride solutions was simulated with the Gaussian-98 program package. The results are used for qualitative explanation of the selective transport of water in comparison with electrolyte in the case of reverse osmosis.     

FT‐IR Investigation into the miscible interactions in new materials for optical devices

In this article we determine the miscibility of azobenzene derivative (poly(4‐(N‐(2‐methacryloyloxyethyl)‐N‐ethylamino)‐4′‐nitroazobenzene)₉₀‐co‐(methyl methacrylate)₁₀)/poly(vinyl acetate) (PVAc) and azobenzene derivative/poly(vinyl chloride) (PVC) blends using Fourier Transform infrared (FT‐IR) spectroscopy. With this method we can clearly identify the exact interactions responsible for miscibility. In the azobenzene derivative 50:50PVAc blend new peaks were evident at 2960, 2890, 1237 and 959 cm^?1, these peaks depict miscible interactions. These wavenumbers indicate that the miscible interactions occurring are from the C? H stretching band, the vinyl acetate C?O, conjugated to the ester carbonyl, the cis‐transformation N?N stretch frequency and the acetate ester weak doublet. The azobenzene derivative 80:20PVC blend display peaks identical in profile to the blend homopolymers, indicating no miscible interactions. However, this could be due to overlapping of peaks within the same wavenumber region, making resolution difficult. This research demonstrates FT‐IR can deduce favorable interactions for miscibility and therefore numerous miscible blends can successfully be calculated if possessing the same groups responsible for miscibility. This paves the way for a new generation of designer optical materials with the desired properties. Copyright © 2003 John Wiley & Sons, Ltd.     

Role of polyethylene‐graft‐glycidyl methacrylate compatibilizer on the biodegradation of poly(ε‐caprolactone)/cellulose acetate blends

Biodegradable polymers provide an attractive solution to reduce environmental pollution caused by the accumulation of plastic waste in landfills. In this study, the effect of polyethylene‐graft‐glycidyl methacrylate (PE‐g‐GMA) on the biodegradation of blends of poly(ε‐caprolactone) (PCL) and cellulose acetate (CA) (80/20, 60/40, 40/60, and 20/80 PCL/CA, w/w) was assessed by mass retention, tensile strength, and morphological properties. The principal fungal strains present in the soil after biodegradation were also identified. PCL and the blends containing 60% and 80% PCL showed greater mass loss and superficial change in simulated soil. PE‐g‐GMA increased the tensile strength retention during 3 months of aging in simulated soil. Scanning electron microscopy (SEM) indicated that pure PCL was more porous, which enhanced the hydrolysis and biodegradation of PCL. PE‐g‐GMA decreased the mass loss of the polymers, possibly by enhancing the interaction between PCL and CA, with the formation of hydrogen bonds between the carbonyl groups of PCL and the hydroxyl groups of CA. This effect was marked in blends with >40% PCL. Microbiological analysis revealed the presence of several species of fungi in the soil. Copyright © 2009 John Wiley & Sons, Ltd.     

The combined effect of wrinkles and noncircular shape of fibers on wetting behavior of electrospun cellulose acetate membranes

Roughness‐induced hydrophobicity is an area of rapid growth which can be achieved through surface texture or surface porosity. Characterizing the effect of surface roughness on wetting behavior of surfaces with irregular shapes has always been a challenging problem. In this work, changing the environmental conditions during electrospinning of hydrophilic cellulose acetate solutions produced highly porous ribbon like fibers, differed widely in their surface morphologies. All samples showed apparent hydrophobicity with water contact angles between 121° and 146°. The specific surface area was introduced for the first time, as a comprehensive parameter to predict contact angles of noncircular fibers. Statistical modeling revealed that the log‐linear models would better fit the data in comparison with the other linear forms. These results confirmed that the specific surface area could be an appropriate single variable for predicting the contact angles of multiscale porous and wrinkled structures of electrospun fibers. Moreover, the membrane produced at 20 °C temperature and the relative humidity of 60% revealed surprisingly high specific surface area (276.63 m²/g) that seems very promising for industrial applications such as separation technologies. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1012–1020     

Thermal,mechanical and morphological analysis of poly(ε‐caprolactone), cellulose acetate and their blends

Poly(ε‐caprolactone) (PCL), cellulose acetate (CA) and their blends were characterized by their tensile strength, differential scanning calorimetry (DSC) and optical microscopy (OM). The compatibility of the blends was investigated and the OM results showed that CA tended to disperse as discrete particles in PCL. Thermal analysis showed the characteristic melting temperature peaks for PCL and CA in all blends, indicating that the compounds were immiscible. The addition of CA to PCL increased slightly the crystallinity of PCL, decreased the elongation at yield and the tensile strength up to 40/60 PCL/CA (w/w), which suggested incompatibility between the polymers. Together, these results indicate the absence of a strong chemical interaction between the two polymers. In agreement with this, the addition of CA to blends with PCL increased Young's modulus. Copyright © 2003 John Wiley & Sons, Ltd.     

Study on the moisture absorption of zwitterionic copolymers for moisture‐sensitive shape memory applications

This study develops a new type of moisture‐sensitive shape memory polymer based on zwitterionic copolymers synthesized with acrylic acid (AA) and 3‐Dimethyl (methacryloyloxyethyl) ammonium propane sulfonate (DMAPS). The moisture absorption properties of zwitterionic copolymers are particularly investigated in this paper. The results demonstrate that the DMAPS/AA copolymers possess a sulfobetaine structure and form a two‐phase separation structure. The zwitterionic copolymers show both good hydrophilic properties and moisture absorption properties. Both AA and DMAPS segments influence the hydrophilic properties and moisture absorption of the composite copolymer. The moisture absorption process is well modeled by Fick's second law in its initial stage. The moisture absorption is mainly determined by immersion conditions and the given materials' structure. Moisture absorption speed and saturated moisture absorption both increase with an increase in DMAPS content as well as the immersion temperature. The increased moisture absorption rate and higher saturated moisture absorption results from the higher activation energy of diffusion. The DMAPS/AA copolymers demonstrate adequate moisture‐sensitive shape memory effects. Stain recovery is faster in the zwitterionic copolymers containing higher DMAPS content, whereas the final shape recovery decreases with an increase of DMAPS content. Finally, it is proposed that not only good moisture absorption units are required but also physical crosslinks should be improved for moisture‐sensitive shape memory polymers. Copyright © 2017 John Wiley & Sons, Ltd.     

A novel orientation technique for semi-rigid polymers. 1. Preparation of cross-linked cellulose acetate and hydroxypropylcellulose films having permanent anisotropy in the swollen state

It has been predicted that unusually good mechanical properties can be obtained by drying swollen networks of semi-rigid chains while they are in the deformed state, as described in several theoretical investigations [Macromolecules,23: 5335, 5341 (1990),24: 901 (1991)]. The present investigation involves the preparation of networks of this type from cellulose acetate (CA) and hydroxypropylcellulose (HPC), in order to test these concepts. The cross-linking required to maintain anisotropy during the drying process was obtained using formaldehyde, while the polymers were in either the anisotropic or isotropic state. Control of the cross-linking was obtained by studying the effects of the concentration of formaldehyde, temperature, and reaction time.The liquid-crystalline phase separations in CA and HPC, and in their networks, were studied with cross-polarized optical microscopy. CA and HPC showed anisotropic phases in trifluoroethanol and in methanol, respectively, and under shear the HPC systems exhibited the band textures associated with macroscopic orientation. In the case of the uncross-linked polymers, this band texture disappeared shortly after shearing was discontinued. The networks prepared by cross-linking the HPC in either liquid-crystalline solutions or in isotropic solutions also showed band textures, but these textures now persisted long after removal of the shearing stress. As shown in the following paper, the extensibility required in the proposed processing technique was highest for the networks prepared in the isotropic state, suggesting that these materials should have the greatest potential for dramatic improvements in mechanical properties.     

Design of an optical sensor for ethylene based on nanofiber bacterial cellulose film and its application for determination of banana storage time

In this work, new ethylene gas sensor was developed on the basis of portable bacterial cellulose (BC) nanofiber film doped with KMnO₄ (K‐BC). The relationship between the concentration of KMnO₄ (8 × 10⁻³, 8 × 10⁻⁴, and 8 × 10⁻⁵ mol L⁻¹) and the optical and morphological properties of ethylene sensor was investigated. The Fourier‐transform infrared results showed that some new interactions have occurred between BC membrane and KMnO₄. The significant reduction in the relative intensity of the characteristic X‐ray diffraction peak of BC in the doped films clearly indicates that the crystalline fraction decreases as a result of KMnO₄ addition. The fabricated K‐BC was used for determination of ethylene concentration. The color, clarity, and absorbance of film at different concentrations of ethylene (10‐2000 μg mL⁻¹) were determined by spectrophotometer. Moisture absorption and water vapor permeability of BC were increased by the addition of KMnO₄. Finally, the ethylene optical sensor was used for detection and determination of ethylene concentration in the bunch banana packages.     

Deformation and fracture behavior of poly(vinylidene fluoride‐trifluorethylene) ferroelectric copolymer films under uniaxial tension

The deformation and fracture behavior under uniaxial tension was characterized for P(VDF‐TrFE) 68/32 mol % copolymer films prepared under two different processing conditions. It was found that the copolymer films prepared by solution casting and then annealing show a typical polymeric brittle fracture feature. For the copolymer films prepared by stretching the solution‐cast films and then annealing process, a typical linearly strengthening stage occurs in the stress–strain curve after yielding, and the polymer film samples fracture at a much larger maximum strain and a higher tensile strength than those prepared by the former process. SEM observation and XRD analysis were carried out to examine the morphology and microstructure change during uniaxial tension. The results show that for the stretched film samples, the polymer chains undergo slipping or further reorientation during uniaxial tension, causing the increase of the peak intensity in the X‐ray diffraction pattern. For the directly annealed ones, no yielding phenomenon is observed and there is no apparent X‐ray diffraction intensity change. It was suggested that the highly‐oriented fibril structure of the stretched film samples contributes to the linearly strengthening stage after yielding in the stress–strain curve. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3255–3260, 2005     

Nonisothermal crystallization and melting behavior of poly(β‐hydroxybutyrate)–Poly(vinyl‐acetate) blends

Nonisothermal crystallization and melting behavior of poly(β‐hydroxybutyrate) (PHB)–poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB–PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB–PVAc blends very well. The double‐melting phenomenon is found to be caused by crystallization during heating in DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 443–450, 1999     

Filling‐level effect on the physical properties of MgBr2‐ and MgCl2‐filled poly(vinyl acetate) films

The structural properties of poly(vinyl acetate) (PVAc) films filled with different levels of MgBr₂ or MgCl₂ were investigated. Differential scanning calorimetry revealed that, at certain filling levels of MgBr₂ or MgCl₂, two new transitions appeared. The first one was due to the α relaxation (T_α) associated with a crystalline region, and the second was due to the melting temperature (T_m). This implies that a crystalline phase was formed in the polymeric matrix. Changes occurring in T_α, T_m, and the melting peak area as a function of the filling level were examined. The X‐ray diffraction (XRD) pattern revealed that the pure PVAc film was amorphous. However, the addition of MgBr₂ or MgCl₂ led to the formation of a crystalline phase in the polymeric matrix that depended on the filling level. XRD also demonstrated that the structural changes depended not only on the metal ions but also on the halide ions. Scanning electron microscopy images for the studied samples were examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 112–119, 2003     

Investigation into new materials for optical devices: the miscibility and solvent effects of azobenzene derivative blends

With the increasing demand for novel devices with optical applications the search for new materials to data store and process becomes a priority. By introducing blends, tailor made properties and low cost give added advantage. Miscibility is an essential requirement for a new material, this research thus involves miscibility studies of poly(4‐(N‐(2‐methacryloyloxyethyl)‐N‐ethylamino)‐4′‐nitroazobenzene)₉₀‐co‐(methyl methacrylate)₁₀, (azobenzene derivative) with polymethyl‐methacrylate (PMMA), polyvinylacetate (PVAc) and polyvinylchloride (PVC) prepared in tetrahydrofuran (THF), and/or dimethylformamide (DMF) and/or dichloromethane (CH₂Cl₂). The glass transitions, solvent and varying molecular weight effect were investigated, since these all primarily influence the miscibility. THF was found to encourage miscibility at specific compositions of PVAc and PVC blends. However, with CH₂Cl₂ and DMF immiscibility is encouraged. The Fox–Flory equation was applied to the blends analyzing the PVC blends in DMF as deviations from ideality. Different molecular weights of PMMA were identified as immiscible regardless of solvent. PMMA's lower solubility in THF and CH₂Cl₂ compared to the azobenzene derivative, displayed the existence of PMMA islands. In all blends the favorable and unfavorable interactions between polymer–solvent–polymer systems are considered. Furthermore, the miscibility effect on increasing the MMA content of the azobenzene derivative was also investigated. Copyright © 2002 John Wiley & Sons, Ltd.     

Investigation of the spectral,optical and surface morphology properties of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide small molecule for optoelectronic applications

The spectral and optical properties of the solutions of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C5) small molecule for different molarities were investigated in detail. The significant spectral parameters such as molar/mass extinction coefficients, absorption coefficient, electric dipole line strength, and oscillator strength of the PTCDI‐C5 molecule were calculated. The absorption bands of PTCDI‐C5 show vibronic structures with seven peaks at 2.08, 2.35, 2.53, 2.70, 2.86, 3.32, and 3.86 eV, respectively. The electronic spectra of the PTCDI‐C5 can be characterized by two basic regions as visible and Soret band. Effects of the molarities on the significant many optical parameters were investigated in detail. The direct and indirect allowed optical band gaps of the PTCDI‐C5 decrease with increasing molarity. Then, surface morphology properties were investigated and calculated roughness parameters of the PTCDI‐C5 film. Finally, we discussed for optoelectronic applications of these parameters, and this study was compared with the similar and related studies in the literature. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of the optical constants of solar‐control amorphous silicon thin films on float glass

An improved method employing a modified Forouhi and Bloomer disperse model with a hybridized simulated annealing algorithm is implemented in this paper, allowing the determination of refractive index, extinction coefficient, and thickness of a‐Si films at one time by fitting reflectance and transmitted spectra. The thickness of films obtained by this method has a reasonable agreement with the result by ellipsometric measurement, especially for samples with thickness in the range of 40–80 nm. The presented method exhibits low time consumption and cost, which implies a possibility of usage in real‐time on‐line measurement of solar‐control coatings on float glass. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

On the basis of stable all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane, a series of alkali metal atom doped M F₆C₆H₆ (M = Li, Na, and K) compounds were theoretically constructed and studied by using ab initio quantum chemistry method. The calculated results show that the HOMO–LUMO gap of the M F₆C₆H₆ conspicuously narrowed from 10.41 eV of pure F₆C₆H₆ to about 2.00 eV of M F₆C₆H₆. The electride characteristics of M F₆C₆H₆ are verified by their electronic structures, HOMOs, and small VIE values. As expected, these electrides possess considerable static first hyperpolarizabilities (β₀). Among the studied electrides, the largest β₀ of the Li F₆C₆H₆ is 7.00 × 10⁵ au, which is about 3030 times larger than pure F₆C₆H₆. TD‐M06‐2X calculations show that these larger β₀ values are attributed to lower transition energies for the crucial excited states of M F₆C₆H₆ systems. Further, the vibrational contributions to the static first hyperpolarizabilities of these molecules are also estimated. Moreover, Li atom doped dimer and trimer of F₆C₆H₆ also present unusual electride's features and exhibit dramatically large β₀. Thus, the F₆C₆H₆ interacting with the alkali metal atoms may be a potential promising NLO nanomaterial.     

Influence of Fe‐MMT on the fire retarding behavior and mechanical property of (ethylene‐vinyl acetate copolymer/magnesium hydroxide) composite

In this work, Fe‐montmorillonite (Fe‐MMT) is synthesized and used as a synergistic agent in ethylene vinyl acetate/magnesium hydroxide (EVA/MH) flame retardant formulations. The synergistic effect of Fe‐MMT with magnesium hydroxide (MH) as the halogen‐free flame retardant for ethylene vinyl acetate (EVA) is studied by thermogravimetric analysis (TGA), limiting the oxygen index (LOI), UL‐94, and cone calorimetry test. Compared with that of Na‐MMT, it indicates that the synergistic effects of Fe‐MMT enhance the LOI value of EVA/MH polymer and improve the thermal stability and reduce the heat release rate (HRR). The structure and morphology of nanocomposites are studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of the EVA composites have also been studied here, indicating that the use of Fe‐MMT reduces the amount of inorganic fillers. MH hence enhances the mechanical properties of the EVA composite while keeping the UL‐94 V‐0 rating. Copyright © 2008 John Wiley & Sons, Ltd.