Surface changes of corona‐discharge‐treated polyethylene films

Morphological and chemical changes of the surface of low‐density polyethylene (LDPE), linear middle‐density polyethylene (L‐MDPE), and their 80/20 blend were studied by different techniques after corona‐discharge treatment in air and subsequent annealing. The surface tension was determined by wetting; the roughness was measured by atomic force microscope (AFM), and the surface chemical composition was analyzed by X‐ray photoelectron spectroscopy (XPS), whereas the low‐molecular‐mass fraction washed off by chloroform by FTIR. The surface tension of the films increases with the electrode current. The surface roughness depends primarily on the polymer type and is less affected by the corona treatment. At the initial stage of annealing, posttreatment‐type oxidation and hydrophobic recovery are competing. The former is more pronounced in L‐MDPE, the latter in LDPE. After annealing at 50°C for 160 days, hydrophobic recovery becomes predominant in each film studied, which is accompanied by significant smoothening of the surface. According to XPS and FTIR results, this is due to the migration of low‐molecular‐mass components (oligomers, oxidized polymer fractions, and additives) to the surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1529–1541, 2000     

The role of surface modification in digital printing on polymer‐coated packaging boards

Digital printing is increasingly being used for package printing. One of the major techniques of digital printing is dry‐toner electrophotography. This paper evaluates the printability of three different extrusion coatings used for packaging boards: low‐density polyethylene (PE‐LD), ethylene methyl acrylate (E/MA) and polyethylene terephthalate (PET). Extrusion coatings in general have an impervious, chemically inert, nonporous surface with low surface energies that cause them to be non‐receptive to bonding with toners. The most common methods used in improving the adhesion properties of polymer coatings are different surface treatments. These increase the surface energy and also provide the polar molecular groups necessary for good bonds between the toner and polymer molecules. The polymer coatings have been modified with electrical corona discharge treatment. The effects of corona on polymer surfaces and the correlation between surface modification and print quality have been evaluated. Results show that sufficiently high surface energy and surface‐charge uniformity are necessary for even print quality and toner adhesion. E/MA and PET have the required surface‐energy level without the corona treatment, but PE‐LD needs surface modification in order to succeed in the electrophotographic process. E/MA also has exceptional surface‐charge properties compared with PET and PE‐LD. Polym. Eng. Sci. 44:2052–2060, 2004. © 2004 Society of Plastics Engineers.     

Optimization of adhesive joints of low density polyethylene (LDPE) composite laminates with polyolefin foam using corona discharge plasma

In this work, surface modification of low density polyethylene (LDPE) film has been carried out to optimize adhesive joints with polyolefin foam for uses in technological applications. LDPE films were modified in a continuous way using corona discharge plasma with different powers, ranging from 200 to 600 W and several film advance rates in the 5–20 m min^?1 range. Changes in surface wettability have been studied with contact angle measurements and subsequent solid surface energy calculation. A polyurethane adhesive was used to join the LDPE film to a polyethylene foam. Mechanical performance of the adhesive joints has been determined by T‐peel tests and also the aging effects of several hydrothermal conditions have been studied to evaluate the usefulness of these laminate composites in technological applications. Results show that corona discharge powers between 400 and 600 W are suitable in terms of wettability improvement; on other hand, a slight decrease in surface wettability as the film advance rate increases is detected but the overall changes as a consequence of the film advance rate in the 5–20 m min^?1 range are small if compared to changes derived from working powers in the 200–600 W range. Adhesive joints offer excellent mechanical performance and good durability in hydrothermal conditions thus being appropriate for technical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface modification of polyethylene by diffuse barrier discharge plasma

Low‐density polyethylene (LDPE) modified by atmospheric dielectric surface barrier discharge plasma in oxygen was investigated to improve surface properties and adhesion of LDPE to more polar polymers. The process of plasma modification was investigated using several methods—surface energy measurements, Fourier Transform Infrared Spectroscopy with Attenuated Total Reflectance (FTIR‐ATR), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The surface energy of LDPE increased significantly after activation by oxygen barrier plasma even at very short time of modification. The FTIR‐ATR spectra manifested the presence of carbonyl functional groups on the surface of polymer pre‐treated by oxygen barrier plasma. It was shown by SEM, and AFM, that the topography of modified LDPE was significantly changed and the surface of modified polymer exhibited higher roughness in comparison with unmodified polymer. The surface energy of treated LDPE diminished in the course of ageing especially during the first 10 days after modification by barrier plasma. Hydrophilicity of the modified LDPE surface was stabilized by photochemical post‐functionalization with 2,2,6,6‐tetramethylpiperidin‐4‐yl‐diazoacetate. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Adhesion of surface‐grafted low‐density polyethylene plates with enzymatically modified chitosan solutions

An investigation was undertaken on application of dilute chitosan solutions modified by tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenetylamine (dopamine) to adhesion of the low‐density polyethylene (LDPE) plates surface‐grafted with hydrophilic monomers. Tensile shear adhesive strength effectively increased with an increase in the grafted amount for methacrylic acid‐grafted and acrylic acid‐grafted LDPE (LDPE‐g‐PMAA and LDPE‐g‐PAA) plates. In particular, substrate breaking was observed at higher grafted amounts for LDPE‐g‐PAA plates. The increase in the amino group concentration of the chitosan solutions and molecular mass of the chitosan samples led to the increase in adhesive strength. Adhesive strength of the PE‐g‐PMAA plates prepared at lower monomer concentrations sharply increased at lower grafted amounts, which indicates that the formation of shorter grafted PMAA chains is an effective procedure to increase adhesive strength at lower grafted amounts. Infrared measurements showed that the reaction of quinone derivatives enzymatically generated from dopamine with carboxyl groups was an important factor to increase adhesive strength in addition to the formation of the grafted layers with a high water absorptivity. The above‐mentioned results suggested that enzymatically modified dilute chitosan solutions can be applied to an adhesive to bond polymer substrates. The emphasis is on the fact that water is used as a solvent for preparation of chitosan solutions and photografting without any organic solvents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improvement in adhesive‐free adhesion by the use of electrostatic interactions between polymer chains grafted onto polyethylene plates

The tensile shear adhesive‐free adhesion properties induced by electrostatic interactions between poly(acrylic acid) (PAA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) chains grafted onto polyethylene (PE) with low‐density (LDPE) or high‐density (HDPE) plates were studied. PAA‐ or PDMAEMA‐grafted PE plates were immersed in a HCl or NaOH solution or water for 24 h, and their electrostatic properties were changed before they were overlapped with each other and heat‐pressed. The breaking of the substrate between the two plates with water‐swollen grafted layers was observed in the low range of grafted amounts in comparison with immersion in the acidic and basic solutions. The ability of the two plates with grafted polymer chains swollen in water to strongly bond with each other was a result of electrostatic interactions formed by positively charged PDMAEMA and negatively charged PAA chains. The breaking of the substrate in the case of adhesive‐free adhesion between quaternized PDMAEMA‐grafted and PAA‐grafted PE plates immersed in the basic solution occurred with lower grafted amounts of PAA. This came from the strong attractive force between dissociated anionic PAA chains and quaternized cationic PDMAEMA chains in the basic solution. In addition, the adhesive‐free adhesion strength of HDPE plates with the same grafted polymer chains encountered the breaking of the substrate with lower grafted amounts than that of LDPE plates. It was concluded that the grafting of polymer chains onto HDPE plates with high crystallinity was considerably restricted to the outer surface regions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2632–2638, 2006     

Adhesion of extrusion‐coated polymer sealing layers to a fiber‐based packaging material with an atomic layer deposited aluminum oxide surface coating

Adhesion of extrusion‐coated polymer sealing layers on an atomic layer deposited (ALD) aluminum oxide (Al₂O₃) surface coating was investigated with a view to gain information on the applicability of ALD deposited barrier layers in fiber‐based packaging materials. The polymers used for the sealing layer were low density polyethylene (LDPE), polyethylene terephthalate (PET), and polylactide (PLA). They were extrusion‐coated onto the ceramic side of paper/PET/Al₂O₃ substrates, where the Al₂O₃ layer was a few tens of nanometers thick. According to the results, good adhesion was obtained for LDPE coating, whereas the other coatings showed a considerable lack of adhesion. Presumably, the oxidation faced by LDPE in the air gap of the extrusion‐coating process was able to create an extensive number of reactive sites that strongly bonded with the hydroxyl groups on the oxide surface of the substrate. With the PET and PLA coatings, such oxidation did not occur and the adhesion obtained remained at a relatively poor level. With all of the coatings, the adhesion levels were improved using corona discharge equipment as a pretreatment prior to the extrusion‐coating process. POLYM. ENG. SCI., 52:1985–1990, 2012. © 2012 Society of Plastics Engineers     

Adhesion of polyethylene plates photografted with methacrylic acid and acrylic acid with enzymatically modified chitosan solutions and X‐ray photoelectron spectroscopy analysis of failed surfaces

An investigation was carried out on the application of dilute chitosan solutions modified by a tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenetylamine (dopamine) to the adhesion of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) plates photografted with carboxyl‐group‐containing hydrophilic monomers, such as methacrylic acid (MAA) and acrylic acid (AA). In the case where photografting was carried out at lower monomer concentrations or at lower temperatures, the adhesive strength sharply increased with lower grafted amounts. A sharp increase in the adhesive strength was found to be due to the formation of shorter grafted polymer chains at lower monomer concentrations and/or the restriction of the location of grafting to the outer surface region at lower temperatures. In addition, the adhesive strength also sharply increased at even lower grafted amounts for photografting onto the HDPE plates and/or that of AA because the location of grafting was restricted to the outer surface region. For the AA‐grafted LDPE and HDPE plates, substrate breaking was observed. This was attributed to the coverage of the substrate surfaces with grafted poly(acrylic acid) chains at lower grafted amounts and a high water absorptivity of the grafted layer. X‐ray photoelectron spectroscopy (XPS) analysis of the grafted LDPE plates incubated in a dopamine solution containing tyrosinase suggested that the increase in the adhesive strength was caused by the penetration of enzymatically modified chitosan solutions in the grafted layers and the subsequent reaction of quinone derivatives enzymatically generated with grafted polymer chains. In addition, the surface analysis of the failed surfaces by XPS showed that as the adhesive strength increased, the location of failure was shifted from the interface between the layers mixed with enzymatically modified chitosan materials and grafted polymer chains to the inside the grafted layer containing enzymatically modified chitosan materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface Silanization of Polyethylene for Enhanced Adhesion

Low density polyethylene has been treated using a novel surface treatment process “SICOR” (“SIIane-on-CORona” treated polymer) in order to enhance adhesion with a range of adhesives including polyure-thane, methacrylate and cyanoacrylate. The process comprises two steps, i.e corona discharge followed by application of an organo-functional silane. The incorporation of surface hydroxyl groups onto the polymer surface enables organo-silane to create the hydrogen or covalent bonds with the oxidized polymer surface. The possibility of the creation of these bonds has been investigated using FTIR, XPS and wettability studies. The adhesion enhancement due to the new process is significant. Frequently, the strength increase exceeds 200% compared with the corona discharge treatment and more than 300% compared with LDPE priming using the “Loctite 770” polyolefin primer. The process is shown to be as good as, or better than, plasma treatment in terms of the strength increase following substrate treatment prior to adhesive bonding.     

Surface modification of low‐density polyethylene films by a novel solution base chemical process

The surfaces of the film samples of low‐density polyethylene (LDPE) were chemically modified with an aqueous solution of ammonium persulphate solution (0.1 M) and Fe (NO₃)_3,9H₂O (0.2 M) heated to about 80°C for 2.5 h for which polar groups like ? OH, 〉CO, ? COOH, etc., were generated on the surface of the LDPE films. The modified films were analyzed by Infrared (IR) spectroscopy, Scanning Electron Microscopy (SEM), and Electron Spectroscopy for Chemical Analysis (ESCA). New surface of LDPE produced by this modification, demonstrated reasonable oxygen incorporation on the surface of polymer films through chemical bonding, which is essential for adhesion processes. For these chemical changes the extent of printability and adhesion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3046–3051, 2004     

Aging and annealing behavior of polycarbonate surfaces modified by direct‐current glow discharge in air

Aging and annealing a polycarbonate (PC) polymer surface treated by direct‐current (dc) glow discharge tend to revert it back to its virgin (pristine) state existing before surface modification by glow discharge. This structural recovery during aging and annealing has been studied in terms of the contact angles of test liquids and surface energy and correlated to the parameters of surface treatment such as the treatment time and power. Samples stored in hydrophobic environments such as air and treated by dc glow discharge at higher power levels show less recovery during aging than those treated at lower power levels. Similarly, a longer exposure time at a power level of 2.04 W decreases the extent of structural recovery in terms of surface energy during aging in air. At higher power levels, the higher kinetic energy of plasma species involved during dc glow discharge results in greater thickness of the damaged layer of the polymer surface, and so a PC sample exposed to dc glow discharge at a higher temperature also recovers at a slower rate during the initial phase of aging, whereas samples with surfaces modified by dc glow discharge at room temperature but annealed at a higher temperature show a relatively rapid recovery during the initial phase of aging. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface degradation and hydrophobic recovery of polyolefins treated by air corona and nitrogen atmospheric pressure glow discharge

The surface degradation and production of low molecular weight oxidized materials (LMWOM) on biaxially oriented polypropylene (BOPP) and low‐density polyethylene (LDPE) films was investigated and compared for two different dielectric barrier discharge (DBD) treatment types, namely air corona and nitrogen atmospheric pressure glow discharge (N₂ APGD). Contact angle measurements, X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) analyses were performed in conjunction with rinsing the treated films in water. It is shown that N₂ APGD treatments of both polyolefins result in much less surface degradation, therefore, allowing for a significantly higher degree of functionalization and better wettability. Hydrophobic recovery of the treated films has also been studied by monitoring their surface energy (γ_s) over a period of time extending up to several months after treatment. Following both surface modification techniques, the treated polyolefin films were both found to undergo hydrophobic recovery; however, for N₂ APGD modified surfaces, γ_s ceases to decrease after a few days and attains a higher stable value than in the case of air corona treated films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1291–1303, 2004     

Influence of ageing on adhesive properties of polypropylene modified by discharge plasma

The adhesive properties of isotactic polypropylene with different degrees of crystallinity, surface‐modified by corona discharge plasma have been studied, during the process of ageing. Considerable decrease in the surface free energy and its polar component was observed. A significant correlation was found between the mechanical work of adhesion to polyvinyl acetate and the polar fraction during ageing. The influence of the crystallinity of the polymer on the resulting adhesion parameters of aged polypropylene foil was confirmed. © 2001 Society of Chemical Industry     

Improvement of the polarity of polyethylene with oxidized Fischer–Tropsch paraffin wax and its influence on the final mechanical properties

The easy, low‐cost modification of the polarity of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) through blending with oxidized Fischer–Tropsch wax was investigated. A 10 wt % concentration of the wax increased the polar component of the total surface free energy 10 times for LDPE and 4.5 times for HDPE. Modified LDPE also had significantly higher adhesion to the polar substrate, which was represented by a crosslinked epoxy‐based resin. This behavior was not observed for HDPE. The conservation of the good mechanical properties of polyethylene was observed. The wax content had only a moderate influence on the mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1164–1168, 2005     

Polymer Self‐Etching for Superhydrophobicity through a Green Hot‐Pressing‐Exfoliation Process: Low and High Adhesion

A green polymer self‐etching strategy for fabricating superhydrophobic surfaces exhibiting low and high adhesion is proposed by using hot‐pressing and exfoliation on a pair of low density polyethylene (LDPE) films. It is demonstrated that the hot‐pressing temperature has significant influence on the surface morphology of LDPE. Effective hot‐pressing temperature for low‐adhesive superhydrophobicity ranges from 109 to 161 °C. Bird's‐nest like micro‐/nanostructures are observed in the unzipped LDPE surfaces compressed at 109 °C, which shows excellent water repellency. LDPE surface compressed at 108 °C demonstrates superhydrophobicity with high adhesion, i.e., a water droplet cannot roll off even when the surface is turned upside down. Furthermore, superhydrophobic vessels are processed and applied to transport water and microdroplets of water losslessly.

     

XPS Studies of Polymer Surface Modifications and Adhesion Mechanisms

XPS has been used to elucidate the mechanisms of surface modification of low density polyethylene by electrical (“corona”) discharge treatment and by chromic acid treatment. The use of derivatisation techniques for improving the precision of functional group analysis is described. These techniques also allow the role of specific interactions in adhesion to discharge treated surfaces to be investigated. The role of residual Cr on the adhesion of deposited metal to polymer surfaces is discussed.     

Surface modification of low‐density polyethylene films by UV‐induced graft copolymerization with a fluorescent monomer

Surface modification of argon plasma–pretreated low‐density polyethylene (LDPE) film via UV‐induced graft copolymerization with a fluorescent monomer, (pyrenyl)methyl methacrylate (Py)MMA, was carried out. The chemical composition and morphology of the (Py)MMA‐graft‐copolymerized LDPE [(Py)MMA‐g‐LDPE] surfaces were characterized, respectively, by X‐ray photoelectron spectroscopy (XPS) and by atomic force microscopy (AFM). The concentration of the surface‐grafted (Py)MMA polymer increased with Ar plasma pretreatment time and UV graft copolymerization time. The photophysical properties of the (Py)MMA‐g‐LDPE surfaces were measured by fluorescence spectroscopy. After graft copolymerization with the fluorescent monomer, the surface of the LDPE film was found to have incorporated new and unique functionalities. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1526–1534, 2001     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

Improvement of adhesion and long‐term adhesive reliability of liquid crystalline polyester film by plasma treatment

Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was examined by low‐pressure plasma treatment to improve initial adhesion and long‐term adhesive reliability between the LCP film and an epoxy bonding sheet for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes as reactive‐ion‐etching (RIE), direct‐plasma (DP) with pressures ranging from 4.0 to 26.6 Pa. Although the initial adhesion of the DP‐treated film increased, the long‐term adhesive reliability estimated by pressure cooker test (PCT) decreased with decreasing the plasma gas pressure in every gas. The higher concentration of the generated polar groups such as phenolic hydroxyl group and carboxyl group enhanced the initial adhesion by the increase in the chemical interaction; however, it damaged the long‐term adhesive reliability due to the acceleration of the penetration of water molecules into the interface. The large surface roughness was effective to enhance the initial adhesion and the long‐term adhesive reliability. The RIE‐treatment generated the polar groups and the larger surface roughness than the DP‐treatment. The RIE‐treatment in the O₂ atmosphere at the gas pressure of 13.3 Pa was the best plasma condition for both the initial adhesion and the long‐term adhesive reliability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Creep and recovery behavior of novel organic‐inorganic polymer hybrids

A novel class of organic‐inorganic polymer hybrids were developed by meltblending up to 50 (v/v) % [about 83 (w/w) %] tin‐based polyphosphate glass (Pglass) and low‐density polyethylene (LDPE) in conventional plastics processing equipment. The creep and recovery behavior of these polymer hybrids at 30°C were studied to understand the effect of the Pglass on the creep resistance of the LDPE. The results suggest that the Pglass acts as a reinforcement and an increase in the Pglass loading leads to significantly lower creep strains. This creep resistance is further enhanced by pretreating the Pglass with coupling agents prior to incorporating them into the Pglass‐LDPE hybrids. The experimental creep compliance of these materials conformed excellently with empirical power‐law equation and a modified Burger's model, suggesting that the materials are linearly viscoelastic under the test conditions.