Morphology and stress relaxation in oriented polyolefin shrink films

Morphology and stress relaxation of oriented polyolefin films has been studied. The influence of orientation on morphology of the films has been investigated using X‐ray, DSC, and TEM. The relaxation time spectrum of oriented films has been investigated. It was shown that relaxation time spectrum of composite film can be predicted if one knows the relaxation time spectrum of each component in the film. An influence of irradiation on relaxation behavior of polyethylene film was shown as well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3424–3429, 2003     

Biodegradation of low‐density polyethylene‐banana starch films

Films were prepared by extrusion using acetylated and oxidized banana starches at different concentrations mixed with low‐density polyethylene, and their biodegradation (buried in soil) at different storage times was studied. Morphological, thermal, and mechanical characteristics of the films after degradation were tested. Films made of acetylated banana starch degraded most rapidly and those prepared with oxidized starch had the slowest degradation time. The type of chemically modified starch plays an important role in degradation of film. Burying the films produced a decrease in degradation temperature at the longest storage time, and there was a longer interval in the films prepared with native banana starch, followed by those made of acetylated starch. The buried in soil films had a broad phase transition and, consequently, an increase in enthalpy. This is due to degradation of amorphous starch zones with an increase in the crystallinity. Electron scanning microscopy analysis revealed greater degradation at longer storage time and a more marked effect in the films made of modified banana starch. Mechanical properties of the films were affected by degradation, and these varied depending on the modified banana starch used. The use of biodegradable polymers such as chemically modified banana starch might be feasible for making films with a high rate of degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Controlled gas‐phase sulfonation of low‐density polyethylene films

In the current research, a highly controllable system operating at low temperatures and for short reaction times is employed for the surface sulfonation of low‐density polyethylene. This system provides the advantages of short reaction times and low reaction temperatures, as compared with previous methods of surface sulfonation. Low‐density polyethylene films were sulfonated at 40°C for time periods ranging from 5 to 30 min. Subsequently, all films were analyzed by SEM, EDX, horizontal ATR–FTIR, surface roughness, and dynamic contact‐angle measurements. Sulfonation was effected at all reaction times. The degree of surface sulfonation increased through 10 min and reached a maximum between 10‐ and 30‐min reaction times with concomitant changes in the physicochemical properties of the material. At 30 min, the film topography changed substantially, indicating that sulfonation was no longer limited to a strictly surface reaction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1865–1869, 2000     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Moisture‐sorption characteristics of starch/low‐density polyethylene films

Moisture‐sorption characteristics of starch/low‐density polyethylene (LDPE) blends were carried out at 27°C for water activity (a_w) from 0.1 to 0.9. The sorption data were used to fit six different sorption isotherm models proposed in the literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for the isotherm models reported in the article lies between 0.1 and 0.4 (monomolecular layer) for the BET model and between 0.3 and 0.9 (multimolecular and capillary condensation layers) for other models. The value of the coefficient of determination (R² = 0.97 ± 0.02) confirms the linear fitting of the equations studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1193–1202, 2002; DOI 10.1002/app.10417     

Stress relaxation and activation volume in tension in β‐glucan and chitosan films

β‐Glucan isolated from baker's yeasts (Saccharomyces cerevisiae) and chitosan films were subjected to stress relaxation tests performed at different prestress levels with the aim to study the activation volume during relaxation and to establish corresponding relaxation models. Apparent activation volume (AAV) was numerically calculated from the slope of the relaxation curve and analyzed in dependence on the stress. The tested films conformed to the standard Cottrell–Stokes' law as a reciprocal proportion between initial AAV and prestress. The validity of the Cottrell–Stokes' law could be extended to the main part of relaxation in β‐glucan films stored in standard conditions and associated power relaxation models were applied on experimental data. This behavior was not observed in the case of chitosan films and β‐glucan films which were long stored under dry conditions. The indicated differences in the inner structure of β‐glucan films were supported by the X‐ray diffraction analysis. In chitosan films, the role of prestress location with regard to the yield point was more considerable than in β‐glucan films. Chitosan films tested beyond the yield conformed to the logarithmic model in the first part of relaxation. POLYM. ENG. SCI., 55:624–633, 2015. © 2014 Society of Plastics Engineers     

Modeling nanoporosity development in polymer films for low‐k applications

The bubble growth dynamics of a polymer supersaturated with CO₂ have been modeled for micron‐size films after nucleation. The model equations are based on the shell model of Arefmanesh, Advani, and Michaelides in which a nucleated bubble is surrounded by a finite concentric shell of polymer supersaturated with gas. Bubbles grow by mass transfer of dissolved gas from this shell. The model is extended to allow for diffusion of dissolved gas out of the shell in addition to diffusion into the bubble. A parametric analysis is performed to examine the effects of film thickness, temperature, diffusivity at the T_g and Henry's law constant. POLYM. ENG. SCI., 45:640–651, 2005. © 2005 Society of Plastics Engineers     

Photobiodegradation of low‐density polyethylene/banana starch films

The effects of the starch content, photosensitizer content, and compatibilizer on the photobiodegradability of low‐density polyethylene (LDPE) and banana starch polymer blend films were investigated. The compatibilizer and photosensitizer used in the films were PE‐graft‐maleic anhydride (PE‐g‐MA) and benzophenone, respectively. Dried banana starch at 0–20% (w/w) of LDPE, benzophenone at 0–1% (w/w) of LDPE, and PE‐g‐MA at 10% (w/w) of banana starch were added to LDPE. The photodegradation of the blend films was performed with outdoor exposure. The progress of the photodegradation was followed by determining the carbonyl index derived from Fourier transform IR measurements and the changes in tensile properties. Biodegradation of the blend films was investigated by a soil burial test. The biodegradation process was followed by measuring the changes in the physical appearance, weight loss, and tensile properties of the films. The results showed that both photo‐ and biodegradation rates increased with increasing amounts of banana starch, whereas the tensile properties of the films decreased. The blends with higher amounts of benzophenone showed higher rates of photodegradation, although their biodegradation rates were reduced with an increase in benzophenone content. The addition of PE‐g‐MA into polymer blends led to an increase in the tensile properties whereas the photobiodegradation was slightly decreased compared to the films without PE‐g‐MA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2725–2736, 2006     

Langmuir and Langmuir–Blodgett films of low‐bandgap polymers

Low‐bandgap conjugated polymers have provided a considerable increase in organic photovoltaic efficiencies, however, an understanding of class‐specific nanostructures, necessary to further improve device qualities, remains scarce. Their self‐assembly and associated electronic behaviors in Langmuir?Blodgett (LB) films are used here to provide relationships specific to each polymer, clarifying their structure?property characteristics. The behavior of two low‐bandgap polymers based on cyclopentadithiophene (PCPDTBT) and dithienosilole (Si‐PCPDTBT) units in the Langmuir trough were investigated and it is shown that it is possible to fabricate nanostructured films of low‐bandgap polymers on solid substrates with the LB deposition technique. The polymers were mixed with amphiphilic molecules at well‐defined concentrations to improve the formation of the LB films. The polymers were also deposited by drop‐casting and LB techniques onto interdigitated electrodes to evaluate their electrical properties, and the LB films were characterized for their optical and morphological properties. It was found that both LB and drop‐cast films of PCPDTBT showed higher electrical conductivities than those of Si‐PCPDTBT. Importantly, LB films resulted in higher electrical conductivities – by an order of magnitude ? compared to their equivalent mixtures with stearic acid in drop‐cast films, although drop‐cast films without stearic acid gave higher conductivities. This fine‐tuning of the molecular architectures of the films is thus demonstrated to directly affect the physical properties and may lead to an improvement in device efficiencies in future applications. © 2018 Society of Chemical Industry     

Bioactive efficacy of low‐density polyethylene films with natural additives

Active packaging can be defined as packaging that includes additives that help to extend the shelf life of food; among the advantages of its use is the possibility to reduce the amount of additives added to the food during processing. The aim of this study was to develop, characterize, and apply active films of low‐density polyethylene, incorporating carotenoid and yerba mate extracts as active additives. Active films were obtained by extrusion and were characterized for water vapor permeability, thickness, color, and mechanical and thermal properties. The effectiveness of the films was evaluated using butter packed in the formulated films. There was a significant reduction in thickness, and mechanical, thermal, and water vapor barrier parameters of the films compared to the control. The concentration of additives directly influenced coloration and antioxidant and antimicrobial action of the films. The formulated films provided protection against oxidative action and inhibition of microbial growth. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46461.     

Thermal oxidation of self‐degradable composite films based on low‐density polyethylene

The effect of the structure of composite extrusion films based on a mechanical blend of low‐density polyethylene and poly(hydroxybutyrate) on the service characteristics and the kinetics of thermooxidative destruction was investigated. The aggregate state of the polymers affected the value of the boundary surface in the blend films. An increase in the latter affected the conformation states of both polymers in the blends. In this case, the strength decreased, the steam permeability increased, and the thermooxidative destruction of the polyethylene matrix during the beginning stages was accelerated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1392–1396, 2004     

Enthalpy relaxation of photopolymerized multilayered thiol‐ene films

Multilayered thiol‐ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub‐T_g aging of 10‐, 21‐, and 32‐layered thiol‐ene films was investigated in terms of enthalpy relaxation. Enthalpy relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell‐shaped enthalpy relaxation distribution having peak maximum at T_g‐10°C of each layer component was observed, resulting in broad distribution of enthalpy relaxation over wide temperature range. In addition, enthalpy relaxation of each layer component in the multilayered thiol‐ene films was significantly accelerated comparing to that of bulk thiol‐ene samples. Dynamic mechanical thermal properties of multilayered thiol‐ene films also showed two and three separated glass transition temperature. However, for 32‐layered thiol‐ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric relaxation of polar aromatics in unoriented and oriented linear low‐density polyethylene

The dielectric behavior of some polar aromatics dissolved in nonpolar unoriented and stretched linear low‐density polyethylene was investigated within the temperature region between 150 and 350 K. The measurements were carried out in the frequency range 1 kHz to 10 MHz. The maximum temperatures and the half widths of the loss tangent peaks depend upon the shape and the polar structure of guest molecules. Stretching the samples induced a shift of the loss tangent to higher temperatures, decreased the height, and increased the width of tan δ peak. The activation energy is also influenced by the type of guest molecules and orientation of polymer matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1278–1282, 2001     

Interfacial adhesion in jute‐polyolefin composites

The interfacial adhesion between four different forms of jute fibers (sliver, bleached, mercerized and untreated) and polyolefinic matrices (LDPE and PP) was studied, as a critical factor affecting the mechanical behavior of these composites. The fiber‐matrix adhesion was estimated by means of the critical fiber length (l_c) and the stress transfer ability parameter (τ); such parameters were obtained by Single Fiber Composite (SFC) tests. Tests were carried out to evaluate the mean tensile strength of the fibers, the mean critical fiber lengths and the stress transfer ability parameter for every fiber‐matrix combination, according to Weibull's statistical method. Thermal‐mechanical characterization of the fibers was also carried out to evaluate the resistance to processing conditions. A limited degradation of strength was observed, which, however, does not preclude the use of jute fibers as reinforcing means in polyolefin based composites. It was found that the adhesion was better in PP‐jute composites than in LDPE‐jute composites. In both cases the results showed that the sliver jute and the untreated jute had better adhesion to both matrices than had the bleached and the mercerized fibers. With both matrices the interface adhesion was in the order: mercerized < bleached < untreated = sliver.     

Novel low‐dielectric‐constant copolyimide thin films composed with SiO2 hollow spheres

A series of copolyimide/SiO₂ hollow sphere thin films were prepared successfully based on bis[3,5‐dimethyl‐4‐(4‐aminophenoxy)phenyl]methane and 9,9‐bis(4‐(4‐aminophenoxy)phenyl)fluorene (molar ratio = 3 : 1) as diamine, and 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride) as dianhydride, with different wt % SiO₂ hollow sphere powder with particle size 500 nm. Some films possessed excellent dielectric properties, with ultralow dielectric constants of 1.8 at 1 MHz. The structures and properties of the thin films were measured with Fourier transform infrared spectra, scanning electron microscope, thermogravimetric analysis, and dynamic mechanical thermal analysis. The polyimide (PI) films exhibited glass‐transition temperatures in the range of 209– 273°C and possessed initial thermal decomposition temperature reaching up to 413–477°C in air and 418–472°C in nitrogen. Meanwhile, the composite films were also exhibited good mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of low‐color polyimide/silica hybrid films

A series of polyimide precursors, poly(amic acid)s, containing propyltrimethoxysliane at two chain ends were prepared from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( I ) with six commercially available dianhydrides, followed by end‐capping with 3‐aminopropyltrimethoxysilane (APrTMOS). A new class of fluorine‐containing polyimide/silica composite films ( III ) with chemical bonds between the fluorinated polyimide backbone and the silica network has been synthesized from the APrTMOS‐terminated precursors with tetramethoxysilane via the sol‐gel process and thermal cyclodehydration. The resultant hybrid films were light‐colored, flexible, and tough. They had high levels of thermal stability associated with high glass‐transition temperatures (>251°C), 10% weight‐loss temperatures in excess of 527°C, and char yields at 800°C in nitrogen higher than 60%. For a comparative study, the analogous nonfluorinated polyimide/silica hybrid films ( III′ ), based on 4,4′‐bis(4‐aminophenoxy)biphenyl ( I′ ), and the neat fluorinated polyimide films ( IV ), based on diamine I , were also synthesized and characterized. The hybrid films of the fluorinated series III showed a higher transparency and less color intensity when compared with the nonfluorinated III′ analogs. They also revealed a lower refraction index and birefringence than pure polyimides ( IV ). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4046–4052, 2007     

Stabilization of low‐density polyethylene films containing metal stearates as photodegradants

The effect of various stabilizer additives on Low‐Density Polyethylene films with a thickness of ca. 40 μm and containing metal stearates was studied. The films were subjected to accelerated aging in a QUV Weatherometer. The apparatus was fitted with A320 lamps and operated on a dry cycle at 63°C and an irradiance of 0.67 W/m². A phosphite (Naugard P) and a phosphate (Alkanox 240P) antioxidant provided good stabilization against UV degradation accelerated by transition metal photocatalysts such as cobalt stearate. These compounds outperformed HALS‐based UV stabilizers and a metal deactivator (Irganox MD 1024) at the concentrations tested. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Oxygen enrichment from air through multilayer thin low‐density polyethylene films

Several multilayer thin low‐density polyethylene (LDPE) films were fabricated by blown thin film having a thickness of 7 μm and an area of 130 cm². They were characterized for their oxygen‐enrichment performance from air by a constant pressure–variable volume method in a round permeate cell with an effective area of 73.9 cm². The relationship between oxygen‐enrichment properties, including oxygen‐enriched air (OEA) flux, oxygen concentration, permeability coefficients of OEA, oxygen, nitrogen, as well as separation factor through the multilayer LDPE films, and operating parameters, including transfilm pressure difference, retentate/permeate flux ratio, temperature, as well as layer number, are all discussed in detail. It is found that all of the preceding oxygen‐enrichment parameters increase continuously with an increase of transfilm pressure difference from 0.1 to 0.65 MPa, especially for the trilayer and tetralayer LDPE films. The oxygen concentration and separation factor appear to rapidly increase within the retentate/permeate flux ratio below 200, and then become unchangeable beyond that, whereas the OEA flux and the permeability coefficients of OEA, oxygen, and nitrogen seem to remain nearly constant within the whole retentate/permeate flux ratio investigated, especially for the monolayer and bilayer LDPE films. The selectivity becomes inferior, whereas the permeability becomes superior, as the operating temperature increases from 23 to 31°C. The highest oxygen concentration was found to be 44.8% for monolayer LDPE film in a single step with air containing oxygen of 20.9% as a feed gas and operating pressure of 0.5 MPa at a retentate/permeate flux ratio of 340 and 23°C. The results demonstrate a possibility to prepare an oxygen‐enriching membrane directly from air, based on the easily obtained thin LDPE films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3013–3021, 2002; DOI 10.1002/app.2331     

New approach for the preparation of nanoporous polyorganosilicate low‐k films

The distribution of pores and the mechanical properties of materials are the key factors in preparing satisfactory low‐k films. In the present study, a kind of silsesquioxane‐polyethylene glycol (SSQ‐PEG) was synthesized and used as a template to make the distribution of pores more even in the low‐k films. The crosslinking density of films could be adjusted by the sol‐gel of tetramethoxysilane/dimethoxydimethylsilane with various proportions. The porosity of films could also be adjusted with different proportions of pendant PEG chains introduced. A dielectric constant as low as 2.1 had been achieved for nanoporous polyorganosilicate films with good tenacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1238–1243, 2007     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000