Thickness-dependent glass transition temperature of hydroxyethyl cellulose thin films based on dielectric properties

Hydroxyethyl cellulose (HEC) thin films with a molecular weight of 720,000 g/mol deposited by thermal evaporation in a thickness range of 250, 500, and 750 nm were measured in a frequency range of 1–10⁵ Hz and a temperature range of 233–373 K for dielectric characterization with increments of 10 K. Dielectric results were used to derive and evaluate the glass transition temperature and ductility, which are essential parameters for structural analysis. Results showed that the thickness of HEC thin films was an effective parameter on dielectric and structural properties. Because of the increasing thickness, the dielectric constant has values between 22 and 143 at 1 kHz, and glass transition temperature and ductility change between 211–175 K and 15–20, respectively. Based on the literature and the compatible results, the main effect of these variations could be dead layers and voids in structure. The effect of the dead layer gave an important idea about the adjustability of mechanical properties of HEC thin films depending on the thickness. In this way, it would be possible to use these thin films deposited from HEC with 720,000 g/mol molecular weight, especially in drug delivery, electrophoresis technologies, biomedical devices, and coverage applications.     

Effect of gamma irradiation on optical and chemical properties of cellulose nitrate thin films

In this work, cellulose nitrate films were irradiated with different doses of gamma irradiations. The gamma irradiation doses were 25, 55, 120, and 170 kGy. The compositional transformation, optical properties, and morphological changes resulted from the gamma irradiation were obtained using different spectroscopic methods. These methods were Fourier transform infrared spectrometry, UV/visible spectrometry, and scanning electron microscope. The surface roughness, as well, for pristine and gamma-irradiated polymer films was determined. The obtained results exhibit changes in the absorbance intensities of the function groups of the irradiated cellulose nitrate films. An induced increase in the UV/visible absorption spectra with increase in the gamma irradiation was observed. A noticeable shifting in the UV/visible spectra toward higher wavelength and decrease in the optical band gap were observed as the gamma irradiation increases. As well, the number of carbon clusters and the activation energy were discussed. The morphological investigation indicates the decrease in the roughness surface with increasing of gamma irradiation.     

Morphological,barrier, and mechanical properties of cassava starch films reinforced with cellulose and starch nanoparticles

A comparative performance study of cellulose and starch nanoparticles on plasticized starch reinforcement has been presented. Starch nanoparticles were obtained by ultrasound and acid hydrolysis, and cellulose nanoparticles were extracted by acid hydrolysis from microcrystalline cellulose and sisal fibers. The nanoparticles were characterized according to the zeta potential, the particle-size distribution, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis. The influence of the addition of these nanoparticles to starch films on the morphology, water vapor permeability (WVP), and mechanical properties of the nanocomposites films were investigated. The cellulose nanoparticles exhibited higher electrical stability than those originating from starch. Acid hydrolysis produced starch nanoparticles with higher crystallinity than ultrasound. All the nanoparticles significantly reduced the WVP. The cellulose nanoparticles significantly increased the tensile strength of the starch films; however, they reduced the flexibility of the nanocomposites. The results of this work support the application of starch and cellulose nanostructures for the development of reinforced biodegradable materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47001.     

Pyroelectric properties of PLT thin films

Pyroelectric properties of PLT thin films prepared by MOD method are characterized. Dynamic pyroelectric responses of the films measured with Chynoweth method are presented. Pyroelectric responses of point and quadruple pyroelectric detectors using PLT20 thin films are measured. One-dimensional heat conduction model is used to analyze the properties of the detectors. requirements to the PLT films used for pyroelectric detectors are proposed.     

Structure and thermomechanical properties of stretched cellulose films

Regenerated and stretched cellulose films were investigated for structure and thermomechanical properties as a potential packaging material. Cellulose films were cast from lithium chloride/N, N‐dimethylacetamide and were stretched up to 30% in a dynamic mechanical analyzer sample holder. Wide‐angle X‐ray diffraction analysis indicated that the orientation factor was significantly increased due to stretching. In addition, the stretched films have a higher resistance to the thermal decomposition from thermo gravimetric analysis. The increased orientation of cellulose crystalline structure by the stretching process also increased the storage modulus of cellulose films characterized by dynamic mechanical analysis, which suggest that mechanical properties of cellulose films could be tuned during the stretching process. The α₂ and α₁ relaxations were found at 240 and 300°C, respectively, which are attributed to the micro‐Brownian motion of segments in amorphous region, and activation energies for relaxations were determined with the stretching levels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric properties of amorphous cellulose acetate-butyrate polymer films

The dielectric constant, loss tangent and AC conductivity of solution grown cellulose acetate-butyrate films of 5μm thickness were studied as a function of temperature (300-450 K) in the frequency range 10 Hz-10 MHz. The decrease in dielectric constant was observed with the increase in frequency as well as with temperature. A loss peak was observed in the dielectric loss spectra and was identified as the β-relaxation peak. The frequency-dependent conductivity was also studied. The results were interpreted in terms of electronic conduction via hopping processes.     

Tensile properties of cellulose fiber reinforced hydroxypropylcellulose films

The tensile properties of cross-linked and uncross-linked composite films (thickness ∼20–35 μm) prepared from Hydroxypropylcellulose (HPC) with incorporation of microcrystalline cellulose fibers (Avicel) were studied. The concentration of fibers in the composites ranged from 0 to 30 w/w% and cross-linked composites were obtained by the reaction of HPC-Avicel mixtures with 1,4-butyldiisocyanate. It was demonstrated that the inclusion of fibers in a HPC matrix produces composites with enhanced mechanical properties that are improved by cross-linking. Mechanical results seem to indicate that the elastic deformation of the cross-linked composites is predominantly dominated by the fiber content while the cross-linking affects mainly the plastic deformation. Maximum values of the Young's Modulus, yield stress and tensile stress were observed at 10 w/w% for the cross-linked and 20 w/w% for the uncross-linked composites. Furthermore cross-linked films with 10 w/w% of fibers present values of yield stress and tensile stress that are in average 15 to 20% higher than those obtained for uncross-linked composites with 20 w/w% of fibers. Studies in Polarizing Optical Microscopy and Atomic Force Microscopy (AFM) seem to indicate that tensile properties of these composites are correlated to the packing of fibers. For the concentration of the utilized cross-linking agent, and for a fiber content of 10 w/w%, an optimal packing of fibers throughout the matrix has been correlated to the minimal difference between the roughness parameters obtained by AFM analysis of the top and bottom surfaces of the films.     

Optoelectronic properties of In-doped SnS thin films

Nanostructured un- and In-doped SnS thin films were deposited on fluorine-doped tin oxide (FTO) substrates via an electrochemical deposition technique. The deposited thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), photoluminescence (PL) spectroscopy and UV–visible spectroscopy. The XRD patterns demonstrated that all deposited thin films are made of polycrystalline SnS particles. The AFM images illustrated a distinct change in the surface topography of the SnS thin films due to In-doping. The PL spectra showed two blue emission peaks and a green emission peak for all samples. Also, they highlighted a PL peak for the In-doped thin films. The incorporation of In-dopant leads to enhance in the optical absorption of SnS lattice. The optical energy band gap (E_g) of the deposited thin films was estimated using UV–vis spectroscopy, which indicated that In-doping decreases the E_g value of SnS thin films by creating defect levels. The photocurrent results demonstrated a higher photocurrent response and photocurrent amplitude for the In-doped SnS samples relative to the un-doped SnS thin film. The Mott–Schottky analysis revealed p-type conductivity for all samples. In addition, the carrier concentration of SnS was increased after In doping. The EIS spectra declared that In-doping improves the rate of charge transfer for SnS thin films. The charge transfer resistance of In-doped SnS decreased compared to the undoped SnS thin film. Finally, according to the J-V characteristics, the conversion efficiency of the In-doped SnS thin films was higher than that of the un-doped SnS sample. Therefore, the optical and electrical performance of SnS thin films were improved due to In-doping.     

Mechanical properties of PECVD thin ceramic films

Silicon dioxide (thickness 350 nm and 969 nm) and silicon nitride (thickness 218 nm) films deposited on silicon substrate using plasma enhanced chemical vapor deposition process were investigated using a Berkovich nanoindenter. The load-depth measurements revealed that the oxide films have lower modulus and hardness compared to the silicon substrate, where as the nitride film has a higher hardness and slightly lower modulus than the substrate. To delineate the substrate effect, a phenomenological model, that captures most of the ‘continuous stiffness measurement’ data, was proposed and then extended on both sides to determine the film and substrate properties. The modulus and hardness of the oxide film were around 53 GPa and 4–8 GPa where as those of the nitride film were around 150 GPa and 19 GPa, respectively. These values compare well with the measurements reported elsewhere in the literature.     

Morphological and thermal properties of photodegradable biocomposite films

Biocomposites containing ultraviolet (UV) radiation absorbing inorganic nanofillers are of great interest in food packaging applications. The biodegradable polylactide (PLA) composite films were prepared by solvent casting method by incorporating 1 wt % of titanium dioxide (TiO₂) and Ag‐TiO₂ (silver nanoparticles decorated TiO₂) nanoparticles to impart the photodegradable properties. The films were exposed to UV radiation for different time periods and morphology of the composite films before and after UV exposure were investigated. The results showed that homogenous filler distribution was achieved in the case of Ag‐TiO₂ nanoparticles. The thermal properties and thermomechanical stability of the composite film containing Ag‐TiO₂ nanoparticles were found to be much higher than those of neat PLA and PLA/TiO₂ composite films. The scanning electron microscopy and X‐ray diffraction studies revealed that the photodegradability of PLA matrix was significantly improved in the presence of Ag‐TiO₂ nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and dynamic mechanical properties of hydroxypropyl cellulose films

Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) were used to characterize the morphology of solvent cast hydroxypropyl cellulose (HPC) films. DSC results were indicative of a semicrystalline material with a melt at 220°C and a glass transition at 19°C (T₁), although an additional event was suggested by a baseline inflection at about 80°C (T₂). Corresponding relaxations were found by DMTA. A secondary relaxation at ?55°C was attributed to the interaction between hydroxyl groups of the polymer and residual diluent. The tan δ peak at T₂ was found to arise from an organized phase, presumably from a liquid-crystal mesophase formed while in solution. Crosslinking with a diisocyanate increased the peak temperature of the two primary relaxations, and resulted in a more clearly defined peak for the T₂ transition. From this behavior it was concluded that both T₁ and T₂ are similar to glass transitions (T_g's) associated with an amorphous component and a more highly ordered phase (due to a residual liquid crystal superstructure) in the HPC bulk.     

Morphological study by TEM on uniaxially oriented thin films of PBT

We prepared uniaxially oriented thin films of poly(butylene terephthalate) (PBT) by applying shear strain to the melt and studied their resulting morphology by transmission electron microscopy (TEM), and could show visually that stacked-lamellar structures are formed in aromatic polyesters. On the basis of crystallographic consideration, we assigned each of the recognized stacked-lamellar structures to a shish-kebab structure or a part of it. In addition, we successfully demonstrated that in one shish-kebab structure all or almost all kebabs (namely, lamellae) have a same crystallographic orientation.     

Physical properties of novel free-standing polymer-nanotube thin films

Novel polymer-nanotube composites have been fabricated by the introduction of polymeric material into the free volume contained in carbon nanotube (CNT) mats grown by chemical vapour deposition. The resulting composite material can then be peeled from the substrate to give a free-standing film, the properties of which are controlled by the nanotubes. The nanotube mat acts as a percolative network resulting in increases in surface and bulk conductivities by factors of 10⁷ and 10⁸, respectively. The presence of CNTs also causes the Young’s Modulus of the polymer film to double. It is shown that the presence of CNTs has no effect on the morphology of the polymer itself.     

Preparation and properties of films and fibers of disordered cellulose

The preparation and properties of films and fibers of highly disordered cellulose are described; the basis of the preparation is the regeneration of cellulose from cellulose derivatives in non-aqueous media. These cellulose are at least 97% hydrogen-bond disordered (as measured by the infrared-deuteration technique), give x-ray diagrams showing poor three-dimensional order, and are practically completely accessible to swelling agents such as water and formic acid. The crystallization of these disordered celluloses is described. The effects on native cellulose of ball milling, mercerization, amine treatment, swelling in acid and salt solutions, and swelling in solutions of potassium hydroxide in non-aqueous solvents are described with reference to changes in fine structure as measured by the infrared-deuteration technique.     

Structure and properties of cellulose nanocomposite films containing melamine formaldehyde

Films of high Young's modulus and low density are of interest for application as loudspeaker membranes. In the present study nanocomposite films were prepared from microfibrillated cellulose (MFC) and from MFC in combination with melamine formaldehyde (MF). The prepared materials were studied with respect to structure as well as physical and mechanical properties. Studies in SEM and calculation of porosity showed that these materials have a dense paper‐like structure. The moisture sorption isotherms were measured and showed that moisture content decreased in the presence of MF. Mechanical properties were studied by dynamical mechanical thermal measurements as well as by tensile tests. Cellulose films showed an average Young's modulus of 14 GPa while the nanocomposites showed an average Young's modulus as high as 16.6 GPa and average tensile strength as high as 142 MPa. By controlling composition and structure, the range of properties of these materials can extend the property range available for existing materials. The combination of comparatively high mechanical damping and high sound propagation velocity is of technical interest. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of electrolyte on electrical properties of thin cellulose acetate membranes

The electrical behavior of thin cellulose-2.5-acetate membranes for chemical semiconductor sensor applications was investigated. The influence of electrolyte on the electrical membrane properties was studied by means of electrochemical impedance spectroscopy. The polymeric membranes can be described using the electrical model of Cole and Cole. The membrane electrolyte distribution equilibria were investigated by means of an absorption–desorption method using conductivity measurements. The desorption kinetics for thin cellulose acetate membranes differ significantly from those of thicker cellulose acetate reverse osmosis membranes because here the rate of the ionic exchange at the membrane interface cannot be neglected. The experimentally determined distribution coefficients were used for the discussion of the electrolyte influence on the electrical membrane parameters. A functional dependence was found between the specific membrane resistance of cellulose acetate membranes and the ionic hydration enthalpy. The effect of electrolyte on the relative permittivity can be explained by a theoretical model. © 1994 John Wiley & Sons, Inc.     

Electronic properties of thermally formed thin iron oxide films

The oxide layer, present between an organic coating and the substrate, guarantees adhesion of the coating and plays a determinating role in the delamination rate of the organic coating. The purpose of this study is to compare the resistive and semiconducting properties of thermal oxides formed on steel in two different atmospheres at 250 °C: an oxygen rich atmosphere, air, and an oxygen deficient atmosphere, N₂. In N₂, a magnetite layer grows while in air a duplex oxide film forms composed by an inner magnetite layer and a thin outer hematite scale. The heat treatment for different amounts of time at high temperature was used as method to sample the thickness variation and change in electronic and semiconducting properties of the thermal oxide layers. Firstly, linear voltammetric measurements were performed to have a first insight in the electrochemical behavior of the thermal oxides in a borate buffer solution. Electrochemical impedance spectroscopy in the same buffer combined with the Mott-Schottky analysis were used to determine the semiconducting properties of the thermal oxides. By spectroscopic ellipsometry (SE) and atomic force microscopy (AFM), respectively, the thickness and roughness of the oxide layers were determined supporting the physical interpretation of the voltammetric and EIS data. These measurements clearly showed that oxide layers with different constitution, oxide resistance, flatband potential and doping concentration can be grown by changing the atmosphere.     

Tribological properties of perfluoralkylethyl methacrylate-polymethyl methacrylate copolymer thin films

Perfluoroalkylethyl methacrylate and polymethyl methacrylate copolymers (FMA/MMA) were synthesized by the atom transfer radical polymerization at various FMA/MMA mole ratios. 5 wt% copolymer solutions were spun cast onto PMMA sheet substrates. The effects of monomer ratio on tribological properties were investigated in terms of the surface energy calculated from contact angles, the dynamic friction, and the wear obtained from multiple scratchings. There is a range of optimum FMA/MMA ratios between (1–5)×10⁻³ in which we attain a minimum dynamic friction. The results obtained are discussed in terms of connections between friction, surface tension, and wear mechanisms.     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties of silk fibroin–microcrystalline cellulose composite films

Silk fibroin–microcrystalline cellulose (cellulose whisker) composite films with varied compositions were prepared by casting mixed aqueous solution/suspensions of the two components. Silk fibroin was dissolved in 10M LiSCN followed by dialysis; a cellulose whisker suspension was prepared by sulfuric acid hydrolysis of tunicate cellulose. Macroscopically homogeneous films were obtained at all mixing ratios. While the Young's modulus of the composite films showed a linear, additive dependence on the mixing ratio, the tensile strength and ultimate strain showed a maximum at a 70–80% cellulose content, reaching five times those of fibroin‐alone or cellulose‐alone films. At the same mixing ratio, infrared spectra of the composite films showed a shift of the amide I peak from 1654 to 1625 cm^?1, indicating the conformational change of fibroin from a random coil to a β structure (silk II) at the whisker–matrix interface. This change seems to be induced by contact of fibroin molecules with a highly ordered surface of cellulose whisker. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3425–3429, 2002