Transport properties and their correlation with the morphology of thermally conditioned polypropylene

Time-lag and static sorption experiments were employed to measure permeability, diffusivity and solubility constants of He, A, and CF₄ in polypropylene films cooled at various rates from the melt and subsequently annealed at varying temperatures near the melting point. While solubility constants in films annealed above 90°C showed the normal variation with the amorphous content of the polymer, solubility constants for all unannealed, quenched films were remarkably constant and independent of the rate of cooling. In fact, all quenched films appeared to have the same amorphous content (ca. 41%). The remaining material is believed to be a mixture of monoclinic and hexagonal crystallinity, the volume ratio of the two being a function of the rate of quenching, and changing on annealing, in favor of the more stable, monoclinic form; the transition occurring rather sharply at 90°C. X-ray diffraction provided supporting evidence for the presence of the hexagonal crystals. The diffusion behavior in crystalline polypropylene is normal and Fickian but instead of the usual decline with increasing crystallinity, diffusivities showed definite enhancement in the case of the annealed films, i.e., the expected monotonic decline of D with increasing crystallinity is not observed. This behavior is attributed to a reduction in diffusional impedance through formation of defects in existing crystallites, as the lamellae thicken, in a manner similar to that observed on annealing of polyethylene single crystals. The apparent activation energies of diffusion were essentially constant and independent of thermal history. This suggests that in a highly crystalline polymer diffusion is not so much impeded by the restricted mobility of chain segments but rather by the extremely small dimensions of the available diffusive pathways. In support of the argument that the transport properties of polypropylene are controlled at a level of microstructure well below the characteristic dimensions of spherulities, it was observed that bulk-crystallized polypropylene has a spherulitic structure whose size and texture do not change significantly on annealing.     

Grafting of acrylamide to nylon-6 by the electron beam preirradiation technique. V. Permeability and selectivity of the grafted membranes to ionic solutes and metabolites

Nylon-6 grafted polyacrylamide (NYgAM) membranes were modified by crosslinking and/or annealing with 65% aqueous solution of formic acid at room temperature. The permselectivity properties of the treated NYgAM membranes to a number of ionic solutes of varying molecular size ranging from HBr to tetrabutylammoniumbromide (Bu₄NBr) were studied in the temperature range of 27–47°C. The temperature dependence of the permeation coefficients through the cross linked membranes indicates an apparent energy of activation of 6.6 and 11.3 kcal/mol for HBr and Bu₄NBr, respectively. In the crosslinked and annealed membranes the corresponding activation energy values were found to range from 4.4 to 5.6 kcal/mol, reflecting the increased water uptake of the annealed membranes. The flux of water and bromide solutes through the 135 μm thick crosslinked and annealed NYgAM membranes at 332% graft yield was found to be approximately equal to that of 18 μm thick cellophane films. The permeability coefficients of urea, uric acid, raffinose, and inulin through the crosslinked annealed NYgAM membranes were determined in order to establish the potential applicability of the modified membranes to clinical separation of metabolites. The flux of all four solutes, especially that of uric acid, through the modified NYgAM membranes at 100% graft yield was found to be higher than through the cellophane films. In addition, the flux of inulin was found to be strongly affected by variation in graft yields.     

Effect of rapid thermal annealing on the properties of zinc tin oxide films prepared by plasma-enhanced atomic layer deposition

The effect of rapid thermal annealing treatments on the microstructure, surface morphology, and optical characteristics of zinc tin oxide (ZTO) films produced by plasma-enhanced atomic layer deposition was investigated. The ZTO films were annealed in oxygen atmosphere for 2 min at four selected temperatures from 500 to 800 °C. The X-ray diffraction showed that the annealing temperature has a great influence on the crystalline characteristics of ZTO films. The film shows complete amorphous structure for as-deposited ZTO film. Meanwhile, the spinel zinc stannate Zn₂SnO₄ was obtained for the samples annealed from 500 to 800 °C, which shows polycrystalline nature. The X-ray photoelectron spectroscopy proved that the annealing process in oxygen gas can effectively can reduce the oxygen vacancy defects in the films. In addition, the photoluminescence spectroscopy manifests an ultraviolet emission with a broad peak range from 345 to 385 nm. Moreover, the ultraviolet luminescence intensity increases continuously with the increase of annealing temperature. Spectroscopic ellipsometry analyses demonstrate that the refractive index of annealed films increases as the increase of annealing temperature, while the extinction coefficient decreases gradually with the increase of annealing temperature in the visible light range.     

Packing effect on latex film formation: a photon transmission study

A photon transmission method has been used to study interdiffusion processes during film formation from hard latex particles. Films with different latex content were prepared separately by annealing poly(methyl methacrylate) (PMMA) particles above the glass transition temperature. The transmitted photon intensity from these films increases as the annealing temperature is increased. Monte Carlo simulations are performed for photon transmission through a rectangular lattice. The increase in the transmitted photon intensity (I_tr) is attributed to the latex content (film thickness) for the annealed film samples. It is observed that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. A negative absorbance coefficient has been measured above the 180 °C annealing temperature. Packing coefficients are obtained for films having various latex contents. © 2000 Society of Chemical Industry     

Influence of annealing on the permeation properties of a thermoplastic elastomer

The use of plastic films with specific diffusion or permeation properties for industrial applications has grown at a considerable rate. Some useful applications are found in medical devices, bioreactors, and combustible fuel storage where polymer films function as separation membranes that allow permeation of different gases at different rates. In this work, the permeation and diffusion properties of a polyester‐based thermoplastic polyurethane (TPU) were investigated. TPU injected and extruded specimens were subjected to thermal treatment (annealing) at 100°C for 20 h. Injected samples were exposed to certain hygrothermal conditions and films were prepared to evaluate the influence of annealing on the permeation of gases. In order to achieve a complete analysis, tests such as differential scanning calorimetry, tensile tests, and Fourier transform infrared spectroscopy were conducted to examine the morphological changes. These were then correlated to the TPU permeation behavior after annealing. Water uptake by the polymer—measured as weight gain—likely indicates an increase in the free volume in the amorphous domains. Similarly, in permeation and water immersion tests, the diffusion rate of gases and H₂O through the TPU was higher for the annealed samples when compared to those without treatment, indicating that diffusion within the polymer is dependent on the postprocessing thermal treatment. POLYM. ENG. SCI., 59:1810–1817, 2019. © 2019 Society of Plastics Engineers     

Gas transport properties of poly(ethylene‐2,6‐naphtalene dicarboxylate) films: Influence of crystallinity and orientation

H₂ and CO₂ transport properties were investigated on semicrystalline poly(ethylene‐2,6‐dicarboxylate naphtalene) (PEN) films and biaxially stretched films and analyzed in terms of solubility and diffusion. The decrease of the permeability observed on the thermally crystallized samples has been described by Maxwell's law. No change of the sorption properties of the amorphous phase has been noticed as a function of the thermal treatment and the evolution of the diffusion coefficient has been related to a tortuosity effect. The low permeability measured on the biaxially stretched film is related to both a change of the free volume sizes distribution and a tortuosity effect. The interesting barrier properties of the biaxially stretched film are kept even after annealing the film at 250°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1849–1857, 2003     

Single and mixed gas diffusion through polyethylene films

In this paper, the results of using a mass spectrometer technique to measure mixed-gas diffusion through polymer films are presented. Mixtures of oxygen, carbon dioxide and nitrogen are diffused through films of polyethylene with different degrees and type of chain branching. It is shown that in the case of pure gases Henry's law applies; the gas concentration is proportional to the partial pressure of gas. It is also demonstrated that there is a reasonable correlation between gas solubilities and the Lennard-Jones force constants, although detailed departures from this behaviour are observed for the different materials.The results show that, in general, the presence of one gas can affect the diffusion and solubility of another, although the solubility and diffusion of carbon dioxide were found to be independent of other gases. In particular, an apparent competition is observed between nitrogen and oxygen in terms of solubility. Moreover, the nature of the interaction between gases depends on the degree of branching and the state of annealing of the polyethylene. Contrary to expectation, it is shown that annealing, whilst increasing the crystallinity, increases the permeability of all gases for the only two samples studied in this regard.     

Toughness measurement and toughening mechanisms of arc ion plating Cr2O3 films treated by annealing

Chromium sesquioxide (Cr₂O₃) films were deposited on Ni-based high-temperature alloy substrates by an arc ion plating technique and then annealed at different temperatures and heating rates. The influence of annealing conditions on the toughness of Cr₂O₃ films was calculated according to spherical indentation tests. The increase in grain size and compressive stress, variety of microstructure and surface morphology, and atom diffusion that resulted from annealing caused toughness variations. The increase in grain size closed micro-cracks along the direction of film growth. Compressive stress and a multi-crystal plane led to cracks caused by indentation that required more energy to break through the film. In the process of indentation, turning, bifurcating, and bridging of cracks on film surface was also able to dissipate energy. Atom diffusion in the process of 1000 °C annealing also played a role in grain boundary toughening. The toughness improvement of Cr₂O₃ film significantly improved friction life.     

Annealing effect of perfluorosulfonated ionomer membranes on proton conductivity and methanol permeability

Perfluorosulfonated ionomer (PFSI) was synthesized and PFSI membranes were prepared via a solution‐cast method and annealed at different temperatures from 150 to 230°C. The annealing effect on water content, proton conductivity, and methanol permeability were reported and discussed. X‐ray diffraction and small angle X‐ray scattering were used to test the structure of the membranes. It was found that annealing increased the proton conductivity of the membranes because heat‐treatment helped to free the sulfonic groups that were buried in the polymer segments and form more organized ionic clusters. Water content and methanol permeability of the annealed membranes decreased with increasing annealing temperature. Simultaneously, annealing induced more compact chain packing structure, which eventually affected the transport of the proton and methanol through these ionomer membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Barrier properties of poly(lactic acid)/cloisite 30B composites and their relation between oxygen permeability and relative humidity

Poly(lactic acid) based nanocomposite films were prepared by melt compounding and subsequent flat film extrusion. After characterizing the nanocomposites with the help of transmission electron microscopy and wide angle X‐ray diffraction to estimate the nanoclay distribution in the matrix material, the oxygen and water vapor permeability of untreated and annealed nanocomposite films were analyzed. A reduction to 34% of both permeability values could be realized by the addition of 6 wt % Cloisite 30B and subsequent annealing to realize maximum crystallinity. Experimental permeability as a function of nanoclay concentration was successfully described by the Tortuous Path Model. In addition, the correlation between oxygen permeability and relative humidity was analyzed for pure PLA and PLA based nanocomposite films. For both untreated films oxygen permeability decreased almost linearly between 0% and 96% RH to approximately 70% of the respective value for the dry sample. Annealed PLA films, on the other hand, showed a similar behavior up to 70% RH but an increase in oxygen permeation for higher moisture content. This is explained by the observed reduction in crystallinity generating more free volume, bringing the system closer to the amorphous case where permeability is generally higher. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44424.     

Electro-optical performances of nanostructured SrTiOx films: The effect of plasma power,Ar/O2 ratio and annealing

The present work evaluates the effects of plasma power and oxygen mixing ratios (OMRs) on structural, morphological, optical, and electrical properties of strontium titanate SrTiO_x (STO) thin films. STO thin films were grown by magnetron sputtering, and later thermal annealing at 700°C for 1 h was applied to improve film properties. X-ray diffraction analysis indicated that as-deposited films have amorphous microstructure independent of deposition conditions. The films deposited at higher OMR values and later annealed also showed amorphous structure while the films deposited at lower OMR value and annealed have nanocrystallinity. In addition, all as-deposited films were highly transparent (~80%–85%) in the visible spectrum and exhibited well-defined main absorption edge, while the annealing improved transparency (90%) within the same spectrum. The calculated direct and indirect optical band gaps for films were in the range of 3.60-4.30 eV as a function of deposition conditions. The refractive index of the films increased with OMRs and the postdeposition annealing. The frequency dependent capacitance measurements at 100 kHz were performed to obtain film dielectric constant values. High dielectric constant values reaching up to 100 were obtained. All STO samples exhibited more than 2.5 μC/cm² charge storage capacity and low dielectric loss (less than 0.07 at 100 kHz). The leakage current density was relatively low (3 × 10⁻⁸Acm⁻² at +0.8 V) indicating that STO films are promising for future dynamic random access memory applications.     

Effect of annealing on the properties of nanostructured CuO thin films for enhanced ethanol sensitivity

Copper oxide (CuO) thin films were grown on glass substrates by low cost spray pyrolysis technique for three different molar concentrations (0.05 M, 0.10 M and 0.15 M), at a substrate temperature of 350 °C, and subsequently annealed at 400 °C for 2 h. The effects of precursor concentration and annealing on the structural, electrical and morphological properties of the crystallized films were investigated. X-ray diffractograms of the films showed the formation of single phase CuO with tenorite structure. The electrical properties of the films like carrier concentration, Hall co-efficient (R_H), mobility and conductivity were studied from Hall effect measurements. The positive values of R_H confirmed the p-type conductivity of the films. Resistivity decreased drastically by two orders of magnitude for the annealed films. The microstructures characterized by a scanning electron microscope for 0.15 M concentration of the precursor revealed that the morphology of the films was substantially affected by annealing. The film surface revealed uniformly distributed cluster of peanut shaped grains after annealing. The response of the as deposited and annealed CuO sensor to low concentration of ethanol (10 ppm) was compared. The annealed CuO film showed higher sensor response than the as-deposited CuO film did. The result suggested that annealing causes significant effect on the sensing performance of CuO to ethanol.     

离子束增强沉积制备p-ZnO薄膜

采用离子束增强沉积技术制备了ZnO薄膜,分析了退火温度、退火气氛对所制备ZnO薄膜的结构、电学特性和发光特性的影响。利用IBED法获得的薄膜p型N-In共掺ZnO薄膜在氮气下退火,随着退火温度的升高,薄膜电阻值先降低后升高,然后再降低。而在氧气下退火,即使退火温度只有400℃,薄膜的电阻很快变大。     

The effect of annealing on mechanical and tribological properties of diamond-like carbon multilayer films

The diamond-like carbon (DLC) multilayer films have been deposited by plasma CVD deposition onSi wafer substrate. The deposited films have then been post-annealed in vacuum at 250 °C for 2 h. Changes in internal stress, hardness, critical load, friction coefficient and wear have been investigated toassess the influence of annealing on mechanical and tribological properties of DLC multilayer films. At the same time, DLC single layerfilms are also deposited and annealed in the same method for a comparison.The results show that there is 28–33% decrease in internal stress and 10–13% decrease in hardness of theDLC single layer films after the anneal treatment. However, for the DLC multilayer films, there is 41–43% decreasein internal stress and less than 2% decrease in hardness. In addition, the annealed DLC multilayer filmhas the same friction and wear properties as that un-annealed film. This result indicates that the anneal treatment isan effective method for the DLC multilayer films to reduce the internal stress and to increase the critical load.The by-effect of the annealing, decrease of hardness and wear resistance of the multilayer film, can be restrictedby the multilayer structure.     

Influence of Heat Treatment on the Optical Properties of Thermal Evaporated SnO<Subscript>2</Subscript> Thin Films

In this investigation, the optical properties of the thermally evaporated SnO₂ films and their dependence on the heat treatment were studied. The transmittance, T (λ), spectra were measured over the spectral range of 0.2 to 0.8 μm for SnO₂ films that were annealed at different temperatures (300, 350, 400, 450, 500, 550 and 600 K) in vacuum for 1h. All films showed high transparency in the visible range and increased with increasing the wavelength. These films have become more transparent after annealing at different temperatures. The optical constants of annealed SnO₂ films were obtained by modeling the measured transmission spectra. The best fit modeling of transmission spectra was obtained by applying Drude and OJL models combined with the effective medium approximation Bruggeman model. Increasing the annealing temperatures decreased both the refractive index and the extinction coefficient of the films. While the optical band gap energy increased from 3.05 to 4.11 eV by increasing the annealing temperature from 300 to 600 K, respectively. Analyzing the refractive index dispersion by using the Wemple-DiDomenico model revealed that the oscillator resonance energy E_o decreased whereas the oscillator dispersion energy E_d increased with increasing the annealing temperature.     

Enhancement of thermoelectric performance of N-type Bi2Te3 based thin films via in situ annealing during magnetron sputtering

In this work, n-type Bi₂Te₃ based thin films were prepared in 300 °C via DC magnetron sputtering, and influences of sputtering power and annealing time on thermoelectric properties of films were investigated. The raise of sputtering power brings about the improvement of deposited rate and enhancement of grain size. Taking the consideration that the large-sized grains are to phonon scattering, we determine the medial power of 30 W as the basic technical parameters for the purpose of further optimizing performance through an in situ annealing process. Subsequently, thin-film treated by in situ annealing process acts out an obvious reduction in electrical conductivity attributed to the decrease in carrier concentration. Especially, the film annealed for 40 min shows an enhancement in the Seebeck coefficient and leads to a maximum power factor 0.82 m W m⁻¹ K⁻² at 543 K.     

Role of annealing temperature on structural and optical properties of zinc oxy-nitride films synthesized by powder vapor transport technique

Zinc oxy-nitride (ZnON) is an emerging semiconductor having tunable energy bandgap (Eg) and refractive index (n). Herein, the effect of annealing temperature on ZnON films synthesized on glass substrates at different (50, 100 and 150 sccm) nitrogen gas flow rates (NGFR) by simple powder vapor transport (PVT) technique is studied. All the synthesized ZnON films are annealed at 300 °C for 60 min. The unannealed and annealed ZnON (Un-&-An-ZnON) films are characterized by XRD, SEM, Raman and UV spectroscopies. XRD analysis confirms the formation of polycrystalline ZnN films and no diffraction plane related to oxide phase. The crystallinity of Un-ZnN films is increased after annealing, however, it is maximum for 100 sccm NGFR. Raman analysis indicates the presence of vibrational modes related to ZnN and ZnO phases, thereby confirming the formation of ZnON films. After annealing, the surface morphologies of Un-ZnON films is transformed from nano-sheets/nano-blocks to rounded nanoparticles. The change in structural and morphological features of ZnON films, associated with annealing temperature causes to create stresses and defects and hence Eg and n. The values of n (1.85–1.87) and Eg (2.6–2.7 eV) of Un-ZnON films are increased to (1.98–2.62) and (3.16–3.25 eV), after annealing, respectively. These inexpensive but high quality ZnON films can be used for semiconducting and optoelectronic devices.     

Effect of real working environment/formation of oxide phase on thermoelectric properties of flexible Sb2Te3 films

Flexible Sb₂Te₃ thin films, for thermoelectric generator applications, were deposited by DC magnetron sputtering. As-deposited films were annealed in air to simulated a realistic operating environment. The oxidation behavior of the films was studied by monitoring their phase change on exposure to air at different temperatures between 50 and 300 °C for annealing times from 1 to 15 h. Oxidation of Sb and Te formed Sb₂Te₄ and TeO₂ phases when annealing above 100 °C and Sb₂Te₃ decomposed into oxide phases at an annealing temperature of 250 °C for 15 h. The thermoelectric performance decreased as the content of Sb₂O₄ and TeO₂ phases increased. These findings show the limitations of Sb₂Te₃ films operating in air without vacuum or a protective environment. We propose that the kinetic growth of oxide formation on the Sb₂Te₃ thin films depend on chemical activation energy and oxygen diffusion through the oxide barrier by the variation of annealing temperature and annealing time, respectively.     

Gas barrier and wetting properties of whey protein isolate‐based emulsion films

The aim of this research was to investigate the effect of rapeseed oil concentration (1–3% w/w) on the water vapor, oxygen and carbon dioxide permeability, water vapor sorption and surface properties of whey protein isolate emulsion‐based films. The water contact angle as affected by oil content, film side and time was analyzed. The effect of temperature (5 and 25°C) on the water vapor permeability (WVP), water vapor sorption kinetics and diffusion coefficient was also studied. The results showed that the incorporation of a lipid phase to whey protein film‐forming solutions was able to decrease the WVP, water hydrophilicity (increasing water contact angle) and water transfer of whey protein films. However, the films containing oil were more permeable to oxygen and carbon dioxide. Significantly higher values of WVP and diffusion coefficient were obtained at 5°C than at 25°C, indicating that storage temperature should be taken into account when designing the composition of edible films and coatings for food applications. POLYM. ENG. SCI., 59:E375–E383, 2019. © 2018 Society of Plastics Engineers     

Diffusion and Permeation of Gases in Fiber-Reinforced Composites

Abstract

The presence of filler in a matrix phase greatly alters and also complicates the diffusion process, making experimental data very difficult to handle analytically. In this study both diffusion and permeability data were obtained in unfilled cellulose acetate films and cellulose acetate films filled with cheese cloth. Cheese cloth being highly permeable, the permeabilities and diffusivities of gases in the filled films are greater than in unfilled films due to reduced effective film thickness for molecular diffusion. A mathematical model has been developed which considers molecular diffusion to occur in that part of the film having no filler, while diffusion through the low-resistance cheese cloth is approximated by convective flow controlled only by the pressure gradient across the thickness of the cheese cloth yarn. The mathematical model predicts permeability values somewhat lower than experiment at low flow rates, but agrees well with experimental permeabilities at higher rates. The poor agreement between theoretical and experimental diffusivities is attributed mainly to errors involving the measurement of time lags. Morphological studies of the composite surfaces and cheese cloth filaments show that the cellulose acetate did not penetrate into the cheese cloth yarn which essentially retains its porous structure in the composite.