High-density Polyethylene Films Research Articles

EFFECT OF VIF ON METAM, CHLOROPICRIN, AND 1,3-DICHLOROPROPENE, ALONE AND IN COMBINATION ON NUTSEDGE POPULATIONS

Previous research has demonstrated stimulation of purple and yellow nutsedge (Cyperus rotundus and C. esculentus) with chloropicrin when applied at rates ranging from 100 to 150 lbs/acre (112 to 168 kg·ha–1) under low or high density polyethylene film mulch. This stimulatory effect has been exploited in research by developing a program of metam application 5 days after application of chloropicrin, thus placing metam in the soil once the tubers have begun to sprout and are most vulnerable. This project was expanded in 2004–05 to include the commercial emulsifiable concentrate formulation of 65% 1,3-dichloropropene and 35% chloropicrin (1,3-D + Pic) and virtually impermeable film mulch as well as high density polyethylene film. The test site was a commercial tomato farm in west central Florida with a heavy infestation of purple nutsedge. Chloropicrin was applied into raised beds through three gas knives, while 1,3-D + Pic and metam potassium were applied in 1 acre inch of water through 2 drip irrigation tubes spaced 10 inches apart and 5 inches from the bed center. Metam was applied 5 days after application of chloropicrin and 1,3-D + Pic. Treatments were applied under both standard high density polyethylene film (Hilex and Bromostop) VIF. Stimulation of nutsedge sprouting and emergence was about the same with either chloropicrin alone or combined with 1,3-D; however, there was some enhancement when applied under VIF. There was a slight improvement in efficacy of metam potassium when applied alone under VIF, contrary to previous results. Application of metam 5 days after application of chloropicrin or 1,3-D + Pic greatly improved nutsedge control over that observed without the subsequent application of metam and VIF improved results to some degree. Producers of drip irrigated crops in Florida can achieve acceptable to excellent nutsedge control using this sequential application technique combined with VIF; however, the addition of a second drip tube on the bed top increases expense by about $125/acre and is not compatible with crops grown with more than a single row on the bed.

Lamellar crystalline structure of hard elastic HDPE films and its influence on microporous membrane formation

The development of hard elastic high-density polyethylene (HDPE) precursor films and its influence on the microporous membrane formation have been investigated. As a first step, the HDPE precursor films with ‘row-nucleated lamellar crystalline’ structure were prepared by applying elongation stress to the HDPE melt during T-die cast film extrusion and subsequently annealing the extruded films. This unusual crystalline structure was analyzed in terms of lamellar crystalline orientation, long-period lamellar spacing, crystallite size, and degree of crystallinity. The processing (melt extension and annealing temperature)-structure (lamellar crystalline structure)–property (hard elasticity) relationship of HDPE precursor films was also investigated. The uniaxial stretching of hard elastic HDPE precursor films induces the bending of crystalline lamellae, which leads to the formation of micropores between them. The observation of morphology and air permeability for the HDPE microporous membranes have revealed that the well-developed porous structures characterized by superior air permeability were established preferably from the precursor films prepared by the high stress levels and the high annealing temperatures. Finally, the relationship between the hard elasticity of HDPE precursor films and the air permeability of corresponding microporous membranes was discussed.

KINETIC MODELINGS OF BROCCOLI COLOR CHANGES DURING CHILLED STORAGE

This work studied the kinetic models of broccoli color changes during storage. The Commission Internationale d'Eclairage ([CIE] International Commission on Illumination)-L*a*b* color system parameters a*, b*, H°, total color difference (TCD), chlorophyll content and yellowness degree were used to determine the color changes under the storage conditions at 0, 5 and 10C. The broccoli ball was packed with high-density polyethylene film. The experimental results showed that the package greatly promoted the activation energy of b* value in broccoli while delaying the respiration peak. The nonlinear regression analysis showed that the rate constants of color parameters b* and TCD were following a first-order Arrhenius-type reaction depending on temperature, and the polynomial model was suitable for the changes of a* and H° value. The observed results demonstrated that the variation of color parameters was in accordance with chlorophyll content and yellowness degree in stored broccoli, suggesting the possibility of a computer-vision system application on the color grading of broccoli.

Preparation and Properties of Biodegradable Multilayer Films Based on Soy Protein Isolate and Poly(lactide)

Multilayer film composed of a soy protein isolate (SPI) inner layer and poly(lactide) (PLA) outer layers were prepared by a simple solvent casting method in order to exploit the advantageous properties of both film materials. Tensile strength and elongation at break of the multilayer film were 17.0 ± 0.3 MPa and 176.9 ± 27.9%, respectively. Especially the tensile strength of the multilayer film increased more than 5-fold compared with that of the SPI film. The mechanical properties of the multilayer film were comparable to those of low-density polyethylene (LDPE) or high-density polyethylene (HDPE) films. The lamination of PLA layers on SPI film also resulted in desirable gas barrier properties of the film with both low water vapor permeability (WVP) of PLA and low oxygen permeability (OP) of SPI. The WVP of the multilayer film [(6.66 ± 0.27) × 10-14 kg·m/m2·s·Pa] decreased 40-fold compared with that of the SPI film, and the OP of the multilayer film [(2.40 ± 0.24) × 10-18 m3·m/m2·s·Pa] decreased more tha...

Versatile wide angle diffraction setup for simultaneous wide and small angle x-ray scattering measurements with synchrotron radiation

Here we present a novel, simple, and versatile experimental setup aimed to perform wide angle x-ray scattering (WAXS) measurements alone or in simultaneous combination with small angle x-ray scattering measurements. The design of the WAXS goniometer allows one to obtain high resolution diffraction patterns in a broad angular range. The setup can incorporate a hot stage in order to evaluate temperature resolved experiments. The performance of the equipment has been verified in the BM16 beam line of the European Synchrotron Radiation Facility with different well known samples such as alumina, isotropic film of high density polyethylene (HDPE), and oriented HPDE fiber.

Nutsedge Control with Drip-applied 1,3-Dichloropropene plus Chloropicrin in a Sandy Soil

An evaluation of the effect of bed width (24, 28, 32, and 36 inches) on the control of a mixed population of nutsedge [yellow nutsedge (Cyperus esculentus) and purple nutsedge (C. rotundus)] was conducted with an emulsifiable concentrate formulation of a 1,3-dichloropropene (1,3-D) and chloropicrin (CP) mixture (1,3-DCP) for application through drip irrigation systems. Beds were mulched with either 1.4-mil-thick virtually impermeable film (VIF) or 0.75-mil-thick high-density polyethylene (HDPE) and 1,3-DCP was applied at 35 gal/acre by surface chemigation or via subsurface chemigation 6 inches deep within the bed. HDPE was more permeable to gaseous 1,3-D than VIF so that 1 day after treatment (DAT), 1,3-D gas concentration at the bed centers under VIF was significantly higher than under HDPE. Dissipation of 1,3-D gas with HDPE occurred within 7 DAT, but dissipation with VIF took ∼10 days. In bed centers, 1,3-D concentrations 1 DAT were in the range of 2.3 to 2.9 mg·L–1 whereas in bed shoulders concentrations ranged from 0.1 to 0.55 mg·L–1. In 2002 and 2003, 1,3-D concentration in shoulders of narrower beds was significantly higher than in the wider beds, but dissipated more rapidly than in wider beds. Lower initial 1,3-D concentrations were observed with HDPE film in shoulders than with VIF and the rate of dissipation was lower with VIF. At 14 DAT, nutsedge plants were densely distributed along bed shoulders (19 to 27 plants/m2) with little or no emergence in the centers of beds (fewer than 5 plants/m2), but with no response to bed width. Nutsedge density increased with time, but the nature of the increase differed with bed width. The most effective nutsedge suppression was achieved with 36-inch beds, which had densities of 11–13 plants/m2 on bed centers and 53 plants/m2 on bed shoulders by 90 DAT. Nutsedge suppression was initially more effective with VIF than with HDPE film, so that no nutsedge emerged in the centers of beds mulched with VIF compared with 2–7 plants/ m2 with HDPE by 14 DAT. On bed shoulders there were 2–7 plants/m2 with VIF and 32–57 plants/m2 with HDPE. Increase in nutsedge density with time was greater with VIF so that by 90 DAT nutsedge densities on bed centers and shoulders were greater than with HDPE in 2002 and the same as with HDPE in 2003. Subsurface chemigation did not consistently improve suppression of nutsedge when compared with surface chemigation. Concentrations of 1,3-D in bed shoulders irrespective of bed width were nonlethal. Initial superior nutsedge suppression with VIF did not persist. Nutsedge control in a sandy soil with 1,3-DCP chemigation is unsatisfactory with one drip-tape per bed.

Crystallization of calcium carbonate on polyethylene γ-radiation-grafted with acrylic acid

The use of high-density polyethylene (HDPE) films grafted with acrylic acid by γ-ray irradiation as a template to control the nucleation and growth of calcium carbonate crystals was attempted. The morphology evolution of crystals formed from supersaturated calcium bicarbonate solution on the grafted HDPE films was observed by scanning electron microscopy, and the interaction between the formed crystals and the grafted HDPE films was revealed by Fourier transform infrared spectroscopy. Results of the characterizations proved that carboxylic acid functional groups on the grafted HDPE films significantly facilitated the heterogeneous nucleation of calcium carbonate crystals, and the distribution of the crystals was in congruity with that of the grafted carboxylic acid groups, as discovered by the atomic force microscopic images. It can be concluded that radiation-induced grafting, a method for functional modification of polymer surfaces, is also an effective means for studying biomineralization.

Acquired biodegradability of polyethylenes containing pro-oxidant additives

Biodegrability of high density polyethylene film (HDPE) and low density polyethylene film (LDPE) both containing a balance of antioxidants and pro-oxidants was studied with defined microbial strains particularly with Rhodococcus rhodochrous and Nocardia asteroides in mineral medium. After an abiotic pre-treatment consisting of photooxidation and thermo-oxidation corresponding to about 3 years of outdoor weathering the samples were inoculated, incubated up to 200 days and during the period their metabolic activities were followed by measuring adenosine triphosphate content. Simultaneously the cultures were also monitored by optical microscopy and FTIR spectroscopy. The first initial phase of fast growth caused by the presence of low molecular extractable compounds was followed by a long period of stabilized metabolic activity suggesting that microorganisms continued to gain energy from the substrate but evidently at a much slower rate. Complementary analysis performed at the end of incubation revealed that during the experiment time biodegradation processes probably affected surface layer of materials only.

Biodegradation of γ-sterilised biomedical polyolefins under composting and fungal culture environments

Polyolefin-based commodities are widely used as biomedical devices and food packaging after γ-sterilisation. The aim of the present work was to study the effect of γ-sterilisation on the biodegradation of polyolefins. Films of isotactic polypropylene, high-density polyethylene and ethylene–propylene (EP) copolymers were sterilised under γ-radiation with doses of 10 and 25 kGy. Neat and sterilised samples were incubated in compost and fungal culture environments. The changes in functional groups, surface morphology and chain scission in polymer chains were characterized by FTIR spectroscopy, SEM and viscometric measurements, respectively. A gradual decrease in intrinsic viscosity [ η] and increase in carbonyl and hydroxyl regions in FTIR spectra were found for the γ-sterilised samples as a function of increasing dose. Polypropylene was found to be more susceptible to both radio-oxidation and biodegradation. It was observed that in case of ethylene–propylene copolymers, extent of γ-sterilisation and/or biodegradation depends on the composition and distribution of comonomers. Important surface erosion was detected by SEM, for higher sterilisation doses, after composting.

Sensitive power compensated scanning calorimeter for analysis of phase transformations in small samples

We have designed and developed a sensitive scanning calorimeter for use with microgram or submicrogram, thin film, or powder samples. Semiconductor processing techniques are used to fabricate membrane based microreactors with a small heat capacity of the addenda, 120nJ∕K at room temperature. At heating rates below 10K∕s the heat released or absorbed by the sample during a given transformation is compensated through a resistive Pt heater by a digital controller so that the calorimeter works as a power compensated device. Its use and dynamic sensitivity is demonstrated by analyzing the melting behavior of thin films of indium and high density polyethylene. Melting enthalpies in the range of 40–250μJ for sample masses on the order of 1.5μg have been measured with accuracy better than 5% at heating rates ∼0.2K∕s. The signal-to-noise ratio, limited by the electronic setup, is 200nW.

Biaxial orientation in HDPE films: comparison of infrared spectroscopy, X-ray pole figures and birefringence techniques

In this study, high-density polyethylene films (HDPE) were produced using different processes (film blowing and biaxial orientation) and processing conditions. The orientation of the films was characterized in terms of their biaxial crystalline, amorphous and global orientation factors using birefringence, Fourier transform infrared spectroscopy (FTIR) using a tilted incidence technique and X-ray pole figures. Evaluation of a simplified FTIR procedure without using the tilted method for the determination of crystalline orientation factors proposed in the literature is also evaluated and assessed. The results indicate that FTIR overestimate the crystalline orientation factors, particularly for the crystalline a-axis. Significant discrepancies are also observed for the b-axis orientation, which may be due to an overlap of the amorphous contribution and/or saturation of FTIR bands. Those differences are larger for films with low orientation, such as blown films. Amorphous phase orientation from FTIR depends on the band used and is not necessarily in agreement with that determined from combination of X-ray and birefringence.

The effect of the molecular orientation on the release of antimicrobial substances from uniaxially drawn polymer matrixes

A new method of controlled release of low molecular weight biocides incorporated in polymer matrixes is described. The molecular orientation of uniaxially drawn biocide doped polymer films is suggested as a significant parameter for controlled release monitoring. Triclosan, a well-established widespread antibacterial agent, has been incorporated into high density polyethylene (HDPE) films that have been subsequently uniaxially drawn at different draw ratios. The molecular orientation developed was estimated utilizing polarized μ-Raman spectra. Biocide incorporated polymer films, drawn at different draw ratios, have been immersed in ethanol–water solutions (EtOH) and in physiological saline. The release of Triclosan out of the polymer matrix was probed with UV-Vis absorption spectroscopy for a period of time up to 15 months. In all cases, although the film surface of the drawn samples exposed to the liquid solution was higher than the undrawn one, the relevant release rate from the drawn specimens was lower than the non-stretched samples depending on the molecular orientation developed during the drawing process. A note is made of the fact that no significant molecular orientation relaxation of the polyethylene films has been observed even after such a long time of immersion of the drawn films in the liquid solutions.

Tear anisotropy in films blown from polyethylenes of different macromolecular architectures

AbstractBlown films of different types of polyethylenes, such as branched low‐density polyethylene (LDPE) and linear high‐density polyethylene (HDPE), are well known to tear easily along particular directions: along the film bubble's transverse direction for LDPE and along the machine direction (MD) for HDPE. Depending on the resin characteristics and processing conditions, different structures can form within the film; it is therefore difficult to separate the effects of the crystal structure and orientation on the film tear behavior from the effects of the macromolecular architecture, such as the molecular weight distribution and long‐chain branching. Here we examine LDPE, HDPE, and linear low‐density polyethylene (LLDPE) blown films with similar crystal orientations, as verified by through‐film X‐ray scattering measurements. With these common orientations, LDPE and HDPE films still follow the usual preferred tear directions, whereas LLDPE tears isotropically despite an oriented crystal structure. These differences are attributed to the number densities of the tie molecules, especially along MD, which are considerably greater for linear‐architecture polymers with a substantial fraction of long chains, capable of significant extension in flow. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 413–420, 2005

Improvement of adhesion between poly(ethylene terephthalate) and polyethylene

Three-layer films were prepared with polyethylene (PE) and poly(ethylene terephthalate) (PET) films as the outer layers and a film of high-density polyethylene (HDPE)/ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer blend as the inner layer using compression molding. E-MA-GMA, an elastomer containing an epoxy functional group, was used as the adhesion promoting agent in the multilayer films. The effects of processing temperature, pressure application time and elastomer concentration on adhesion were investigated. The adhesion strength between PE and PET films increased with increasing bonding temperature, bonding time and elastomer concentration. From contact angle measurements, it was observed that the work of adhesion between the polymers increased with increasing amount of elastomer. Improved adhesion between PET and HDPE with 30% elastomer films was confirmed by SEM analyses of the film layers. Using FT-IR analysis of PE/HDPE-30% elastomer/PET delaminated film, the decrease in peak intensity of the epoxy groups tends to indicate reaction of epoxy functionality with functional groups in PET.

Two-dimensional (2D) correlation coefficient analyses of heavily overlapped near-infrared spectra

Two-dimensional (2D) correlation coefficient analysis is employed to classify and characterize spectral variations among heavily overlapped near-infrared spectra of pellets and films of three kinds of polyethylene (PE), high-density (HD), low density (LD), and linear low-density (LLD) polyethylene, and five kinds of ivory signature seals. The sample-sample (SS) 2D correlation maps are used for classification while the wavenumber-wavenumber (WW) 2D correlation maps are used for determining spectral variation among the above materials. Both correlation maps are obtained by multiplying the original data with themselves. It is found that the NIR spectra of pellets and films of HD PE are clearly different from those of LD PE and LLD PE, while the NIR spectra of five kinds of ivory seals yield easily discernable squares in the SS correlation maps. The background variation is thought to be behind the differentiation of the PE samples because the WW correlation maps do not indicate appearance of new bands. The correlation results are compared with those of principal component analysis (PCA). This study is a novel application of 2D correlation coefficient analysis which reveals that a comprehensive description of demanding spectral systems is achievable by utterly simple mathematical means because 2D correlation maps are obtained via a single mathematical operation.

Solubility and Permeability Properties of Edible Pectin-Soy Flour Films Obtained in the Absence or Presence of Transglutaminase

The permeability characteristics and water-solubility of edible pectin–soy flour films obtained in the absence or presence of the enzyme transglutaminase were investigated and compared with those possessed by both the commonly used high density polyethylene film and the biodegradable Mater-Bi® film. The soy protein transglutaminase-catalyzed crosslinking was found to determine a marked decrease in the solubility of the pectin–soy flour films both at different pH and in different denaturing conditions with respect to the films obtained in the absence of the enzyme, even though their solubility remains higher than that of the commercially available polyethylene and Mater-Bi® films. Transglutaminase treatment was also shown to significantly increase pectin–soy flour film barrier properties to oxygen, carbon dioxide and water vapour. In particular, the films obtained in the presence of the enzyme exhibited a permeability to oxygen and carbon dioxide even lower than that possessed by polyethylene films. Our results suggest a possible use of the transglutaminase-polymerized pectin–soy flour films as wrapping of food products requiring a packaging allowing low gas exchange with the environment. Furthermore, the application of these films as coatings to conventional oral dosage forms could provide a viable means of delivering drugs to the colon.

Ultraviolet light treatment of thin high‐density polyethylene films monitored with a quartz crystal microbalance

AbstractUltraviolet (UV) treatment is an effective method for modification of the surface properties of polymeric materials. In this study, the effects of the ozone‐generating UV light treatment of thin high‐density polyethylene (HDPE) films were monitored with the quartz crystal microbalance (QCM) technique both in the presence of ozone and without it. The films were further characterized by X‐ray photoelectron spectroscopy, optical microscopy, and atomic force microscopy. We found that the ozone not only modified the surface properties of the HDPE films but also etched away the polymer layer. An average etching rate of 0.48 nm/min was determined. UV light exposure of the polymer film in an argon atmosphere resulted only in minor degradation of the films; the presence of ozone was needed to cause the destruction and loss of material. The QCM technique was a straightforward method for the monitoring of the kinetics of the ablation induced by the UV–ozone treatment process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2833–2839, 2004

Enzyme-mediated radical initiation of AM graft onto the HDPE film

The mechanism of the enzymatic grafting of high-density polyethylene (HDPE) films with acrylamide compounds was studied. The potential for using horseradish peroxidase (HRP) to graft acrylamide onto the surface of HDPE films was examined. Several analytical approaches provided evidence that the chemical composition and morphology of HDPE surfaces were changed after grafting. Results show that the surface of treated films becomes rougher than the untreated surface. Compared to unmodified HDPE, modified HDPE surface had significantly increased absorbance in the UV-visible region, and the N–H and carbonyl-stretching regions in the IR spectra. The hydrophilicity of treated and untreated HDPE films was analyzed by staining and contact angle measurements. The decreased contact angle of the HDPE film with water and increased adsorption ability of the surface to a water-soluble dye clearly indicated that enzymatic grafted acrylamide could significantly increase the hydrophilicity of the surfaces of HDPE films. Moreover, the hydrophilicity of treated film depend upon the monomer concentration, the initiator concentration and oxidizing agent concentration as well as the time of the reaction, its optimum value appears when the monomer concentration, the initiator concentration, H2O2 concentration and the reaction time were 0.15M, 3.0×10−2M, 6.0×10−3M, and 300min, respectively.

Stabilization of film casting by an encapsulation extrusion method

A film casting simulation has been used to demonstrate why the encapsulation extrusion coating process is so effective industrially in enhancing the stability of the extrusion coating of low-melt-strength polymers. In the present study, it is particularly intended to explain theoretically why and how the co-extrusion of high-melt-strength polymers like low-density polyethylene (LDPE)—attached at the periphery using encapsulation dies—dramatically improves the film coating process of low-melt-strength polymers like high-density polyethylene (HDPE). The undesirable neck-in and draw resonance phenomena frequently occurring in the extrusion coating of HDPE are shown in this study to be due to the fact that lower axial tension in the HDPE film rendered by its low melt strength leads to process instabilities. High melt strength LDPE will then increase the film tension when externally-attached, and as a result improves the stability of HDPE extrusion coating.

Novel surface modification of high‐density polyethylene films by using enzymatic catalysis

AbstractThe surface of high‐density polyethylene (HDPE) films was modified by an enzyme, soybean peroxidase (SBP). The enzymatic surface modification was performed using a peroxidase as catalyst and hydrogen peroxide as oxidizing agent. The chemical composition and morphology of HDPE surfaces were characterized by X‐ray photoelectron spectroscopy, infrared spectroscopy, and scanning electron microscopy. Results showed that after enzymatic treatment, the O/C atomic ratio of HDPE surfaces increased, and new functional groups such as –CO– appeared. Moreover, the surface of treated HDPE films became rougher than untreated surfaces. The hydrophilicity of treated and untreated HDPE films was analyzed by UV–vis spectroscopy and contact angle measurements. The decreased contact angle of the HDPE with water and increased adsorption ability of the surface to a water‐soluble dye clearly indicated that enzymatic treatment can significantly increase the hydrophilicity of the surfaces of HDPE films. The catalytic mechanism of SBP was also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3673–3678, 2004