Characterisation of flame retardant plasma polymer deposited BOPP film

Abstract

Flame retardancy of polypropylene films was studied by plasma polymerisation technique. The surface of BOPP film was modified by boron containing plasma polymers at different plasma conditions. Plasma polymer coated polypropylene films were examined by flame retardancy test (limiting oxygen index, LOI) and TGA. Boron containing plasma polymer deposition on the film surface showed an improvement of flame retardancy. Furthermore, TGA thermograms pointed out that the first degradation temperature of treated polypropylene film was increased from 331 to 396°C, and the second degradation temperature was shifted from 401 to 455°C. Also, the plasma polymers were characterised by FTIR spectroscopy and XPS. According to XPS results, the BOPP surfaces treated with TMB showed significant difference in the composition with respect to the untreated sample. The FTIR spectra of plasma polymers obtained indicated that when the treatment time was increased to 60 min with a constant discharge power at 80 W, the absorption intensities of all the functional groups increased. As a result, boron containing plasma polymer treatment was found to be an effective method in enhancing the flame retardancy of BOPP film.     

Grafting sulfobetaine monomer onto silicone surface to improve haemocompatibility

Silicone rubber has been used as a biomaterial for more than two decades and displays good mechanical and optical properties, but its chemical nature, poor antithrombogenicity, as well as its hydrophobicity, prevents its use in many demanding biomedical applications. In order to provide modified silicone with enhanced haemocompatibility, surface modification techniques were used. Ozonization was used to introduce active peroxide groups onto the silicone film surface and, subsequently, graft polymerization of N,N′‐dimethyl‐N‐methacryloyloxyethyl‐N‐(3‐sulfopropyl) ammonium (DMMSA), a zwitterionic sulfobetaine structure, onto the ozone activated silicone surface was conducted. Surface analysis was accomplished by means of attenuated total reflectance‐Fourier‐transform infrared (ATR‐FTIR), and X‐ray photoelectron spectra (XPS), and scanning electron microscopy (SEM) and contact angle measurement. ATR‐FTIR and XPS investigation confirmed the graft polymerization. The grafted film possessed a relatively hydrophilic surface as indicated by contact angle measurement. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet‐rich plasma (PRP) and protein adsorption in bovine fibrinogen using silicone film as the reference. No platelet adhesion was observed for the grafted films incubated in PRP for 120 min. The protein adsorption was reduced on the grafted films after incubated in bovine fibrinogen for 120 min. These results confirmed that the improved blood compatibility was obtained by grafting this new zwitterronic sulfobetaine structure onto silicone film. Copyright © 2003 Society of Chemical Industry     

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     

Hydrophilic surface modification of polypropylene films by CCl4 plasma

The CCl₄ plasma treatment of polypropylene films was investigated from the viewpoint of hydrophilic surface modification using a contact-angle meter, ATR FTIR spectroscopy, and angular XPS. Hydrophilicity and chemical composition of the CCl₄ plasma treatment was effective in hydrophilic modification. The advancing contact angle of water for polypropylene films was decreased from 99° to 81-7° by the CCl₄ plasma treatment, and the surface energy increased from 27.2 to 38.9-67.7 mJ/m² when the discharge current varied from 50 to 150 mA. The CCl₄ plasma initiated chlorination, oxidation, and aluminum sputtering reactions. The chlorination of polypropylene films was favorable in a mild CCl₄ plasma operated at discharge current of 50 mA. The oxidation and aluminum sputtering reactions were predominant over the chlorination in strong CCl₄ plasmas operated at discharge currents of more than 75 mA. The chlorination initiated by the mild CCl₄ plasma was restricted near the film surface within 36 Å deep. The regions modified with the strong CCl₄ plasma reached inner layers of 36-49 Å deep. Hydrophilicity caused by the CCl₄ plasma treatment may be due not only to chlorine functionalities but also to oxygen and aluminum functionalities. © 1993 John Wiley & Sons, Inc.     

Study of crater structure formation on the surface of biaxially oriented polypropylene film

Biaxially oriented polypropylene (BOPP) film accounts for a large amount of polypropylene since it is well suited for food packaging films or industrial films, because of its high performance in terms of mechanical and optical properties. Recently machine speed has been increasing to obtain higher production rate and film thickness has become thinner to reduce the environmental load. To meet the demands, many researchers have been investigating stretchability of PP by connecting the stretching force at the yield point and crystalline structure. Many other studies have been conducted regarding the surface structure of BOPP. Although there were some cases that crater‐like film surface roughness was formed on BOPP films, the formation mechanism of craters has not been clarified. In this report, new hypothesis of the crater‐like film surface roughness formation mechanism is proposed by observing the transformation of crater from sheet to BOPP film and by investigating the relationship between the stress–strain curve and surface roughness change. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of low-pressure O2 and Ar plasma treatments on the wettability and morphology of biaxial-oriented polypropylene (BOPP) film

Low-pressure plasma treatments in an rf discharge of O₂ and Ar were employed to introduce polar functional groups onto the biaxial-oriented polypropylene (BOPP) surfaces to enhance the wettability and activation. The effects of plasma treatment on the morphology and wettability of the BOPP films were characterized using static contact angle measurements, attenuated total reflection (ATR)–FTIR spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM).     

Control of well‐defined crater structures on the surface of biaxially oriented polypropylene film by adding nucleators

While it is common to add anti‐blocking agents to biaxially oriented polypropylene (BOPP) films for general use in order to prevent blocking against each other, the technology of crater‐like film surface roughness formed on the BOPP films without any additives is well known in the industrial BOPP film areas. Numerous studies have been reported on the crater‐like film surface roughness on the BOPP films since the 1980s, but its formation mechanism and the controlling method of the crater‐like film surface roughness are yet to be clarified. In our previous reports, we presented a new hypothesis of crater formation mechanism from a new point of view on sheet morphology and crater shape on the BOPP film surface. It was strongly influenced by the crystal grain shape in the surface layer of PP sheet. In this report, it was clarified that a nucleator has a big influence on the formation of the crystal grains in the surface layer of PP sheets and on the formation of craters. In addition, craters did not form on the BOPP films stretched from the sheet of which the skin layer with crystal grain was shaved, even though β crystal still remained. It was clarified that the crystal grain is trans‐crystal from the observation using TEM. Therefore, it is concluded that the existence of β crystals in the surface layer of PP sheets is not essential in order to produce craters on BOPP films, but trans‐crystals are necessary to form the craters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3555–3564, 2013     

Surface structure and adhesive properties of biaxially oriented polypropylene film grafted with poly(acrylic amide) using corona discharge

Corona discharge was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene (BOPP) film. The active species formed in air was used to induce graft copolymerization of acrylic amide (AAM) in aqueous solution. The surface structure, hydrophilicity and adhesion of the grafted BOPP film were characterized by the extent of grafting, electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), peel strength and contact angle measurements. Surface graft‐copolymerization of AAM onto BOPP film by corona discharge in air can be carried out with high efficiency. With increasing copolymerization time, the degree of grafting of AAM onto BOPP increases. The degree of grafting achieved a relatively high value of 2.13 wt% for the conditions of 1 min corona discharge and a copolymerization reaction time of 2.5 hr in 20% AAM aqueous solution at 70°C. After corona discharge grafting, the contact angle of water on the BOPP film decreased and the peel strength increased compared with those for ungrafted BOPP film. The hydrophilicity and adhesion of BOPP were improved by surface graft copolymerization with AAM induced by corona discharge.     

Structure and composition of the surface of urethane/acrylic composite latex films

Polyurethane dispersions were prepared and urethane/acrylic composite latices were synthesized with polyurethane dispersions as the seed, and core‐shell emulsion polymerization. Fourier‐transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR) analyses showed that the films obtained from the composite latices were rich in polyurethane component or segments at air‐facing and substrate‐facing surfaces, in comparison with their average composition. Moreover, the substrate‐facing surface contained even more polyurethane component or segments than the air‐facing surface. X‐ray photoelectron spectroscopy (XPS) detection also indicated that the polyurethane component or segments preferentially migrated to the surface layer of the films from the bulk, and that the films from blend latices displayed more polyurethane component or segments near the surface layer. Both FTIR‐ATR and XPS analyses suggested that some reorientation had happened in synthesizing the composite latices and/or after film formation. This structure and composition endow urethane/acrylic composite films with both surface properties (such as mar‐resistance, adhesion, wettability) from pure polyurethane, and film hardness from acrylic copolymers. © 2001 Society of Chemical Industry     

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     

Improvement of performance of polyamide reverse osmosis membranes using dielectric barrier discharge plasma treatment as a novel surface modification method

In this research, surface modification of aromatic polyamide thin film composite (TFC) reverse osmosis (RO) membranes was carried out using dielectric barrier discharge (DBD) plasma treatment to improve the performance and fouling resistance of prepared RO membranes. First, polyamide TFC RO membranes were synthesized via interfacial polymerization of m‐phenylenediamine and trimesoyl chloride monomers over microporous polysulfone support membrane. Next, the DBD plasma treatment with 15 s, 30 s, 60 s, and 90 s duration was used for surface modification. The surface properties of RO membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), SEM, AFM, and contact angle measurements. The ATR‐FTIR results indicated that DBD plasma treatment caused hydrogen bonding on the surface of RO membranes. Also, the contact angle measurement showed that the hydrophilicity of the membranes was increased due to DBD plasma treatment. The changes in the membranes surface morphology indicated that the surface roughness of the membranes was increased after surface modification. In addition, it was found that the DBD plasma treatment increased the water permeation flux significantly and enhanced sodium chloride (NaCl) salt rejection slightly. Moreover, the filtration of bovine serum albumin revealed that the antifouling properties of the modified membranes had been improved. POLYM. ENG. SCI., 59:E468–E475, 2019. © 2018 Society of Plastics Engineers     

Investigation on the oxidation of surface layers of polyolefins treated with corona discharge

The results of an X-ray photoelectron spectroscopic investigation of the oxidation of surface layers of low-density polyethylene (LDPE) and biaxially oriented polypropylene (BOPP) films are presented. The analysis was performed using different take-off angles, namely 10°, 30°, and 90°; thus, the depths of the examined layers were 0.6, 1.9, and 3.7 nm, respectively. It was found that the course of the oxidation process in the surface layers was similar for both polymer films. However, for treatment energies lower than 5 kJ/m², the extent of the oxidation was higher for the LDPE film, whereas for energies above this value, the BOPP film was more oxidized. As detected by X-ray photoelectron spectroscopy (XPS), desorption of oxygen from the film surface occurs for both polymers during the treatment.     

Influence of incorporation of ZnO nanoparticles and biaxial orientation on mechanical and oxygen barrier properties of polypropylene films for food packaging applications

In this work, the effect of zinc oxide (ZnO) concentration and shape on processing and properties of new biaxially oriented polypropylene (BOPP)‐ZnO nanocomposites was studied. The use of spherical nanoparticles and nanorods was expected to differently influence the properties of the final material. Films of isotactic polypropylene prepared with different ZnO incorporation were biaxially oriented under conditions of temperature and strain rate that were similar to those encountered in a commercial film process. Scanning electron microscopy analysis was performed to visualize the dispersion degree of the ZnO nanoparticles in the polymer matrix and to observe the surface and the orientation of the elongated nanoparticles. Furthermore, the prepared ZnO‐BOPP nanocomposites were evaluated for both mechanical and oxygen barrier property enhancement. A good combination of mechanical and oxygen barrier properties was obtained for the ZnO‐BOPP films. This result makes the ZnO‐BOPP nanocomposite a proper material for applications such as food packaging. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Simultaneous graft copolymerization of 2‐hydroxyethyl methacrylate and acrylic acid onto polydimethylsiloxane surfaces using a two‐step plasma treatment

Acrylic acid (AAc) and 2‐hydroxyethyl methacrylate (HEMA) mixtures were simultaneously grafted onto the surfaces of polydimethylsiloxane (PDMS) films using a two‐step oxygen plasma treatment (TSPT). The first step of this method includes: oxygen plasma pretreatment of the PDMS films, immersion in HEMA/AAc mixtures, removal from the mixtures, and drying. The second step was carried out by plasma copolymerization of preadsorbed reactive monomers on the surfaces of dried pretreated films. The effects of pretreatment and polymerization time length, monomer concentration, and ratio on peroxide formation and graft amount were studied. The films were characterized by attenuated total reflection Furrier transformer infrared (ATR‐FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), zeta potential, surface tension, and water contact angle measurements. The ATR‐FTIR spectrum of the modified film after alkaline treatment showed the two new characteristic bands of PHEMA and PAAc. Both increase the polar part of surface tension (γ_p) after grafting and the evaluation of surface charge at pH 1.8, 7, and 12 confirmed the presence of polar groups on the surface of grafted films with a mixture of HEMA/AAc. Morphological studies using both AFM and SEM evaluation illustrated various amounts of grafted copolymer on the surface of PDMS films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhanced dielectric properties of sandwich-structured biaxially oriented polypropylene by grafting hyper-branched aromatic polyamide as surface layers

This work represents multilayer films with sandwich structure by grafting hyper-branched aromatic polyamide (HBP) on both sides of biaxially oriented polypropylene (BOPP) (HBP BOPP HBP). BOPP serves as the middle layer to offer high breakdown strength and HBP acts as surface layers to boost the dielectric constant. As a result, the dielectric constant increases significantly from 2.2 of control BOPP to 5.5 (almost increased 1.5 times) after grafting 2.06 μm HBP surface layers, while the dielectric loss still remains at a very low level (<0.03). In addition, all HBP BOPP HBP sandwich-structured films show higher charge energy density than that of unmodified BOPP. For instance, the discharge energy density of HBP BOPP HBP (1-20-1) film is up to 2.38 J/cm³ at an applied electric field of 400 kV/mm, which increases about 36% over that of pure BOPP (i.e., 1.75 J/cm³). Meanwhile, charge–discharge efficiency retains about 90%. This work offers a simple strategy to fabricate polymer-based high performance dielectric composites.     

Characterization of an amorphous surface layer on blown polyolefin film

This study concerned an amorphous surface layer on blown polyethylene film with a composition different from that of the bulk. The surface layer was characterized by gentle probing with an atomic force microscope. The demonstration of an amorphous layer uniformly covering the surface of a blown Ziegler–Natta‐catalyzed polyethylene (znPE) film reproduced previous reports. Removing the surface layer by solvent washing confirmed the hypothesis that the layer consisted of lower molecular weight, higher branch content fractions. A blown film of znPE blended with up to 30 wt % impact‐modified high‐melt‐strength polypropylene (hmsPP) also exhibited an amorphous surface layer. In thin films, it was advantageous for the mobile, amorphous fractions of ethylene–propylene rubber (EPR) to locate at the surface rather than at the phase interface. The amorphous EPR tended to segregate into pools on the film surface, and this pointed to a substantial difference between the amorphous surface layers on the znPE and hmsPP/znPE blend films. Surface enrichment best described the compositional gradient that resulted from the concentration of lower molecular weight, higher branch content chains at the surface of the znPE film. Surface segregation was more appropriate for the emergence of EPR fractions as a separate phase on the surface of the hmsPP blend film. Films blown from a blend of a Ziegler–Natta‐catalyzed polyethylene and a metallocene‐catalyzed polyethylene (zn/mPE) and its blend with hmsPP reproduced the primary features of surface enrichment and surface segregation. Some differences between the znPE and zn/mPE films were attributed to the metallocene constituent of zn/mPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3625–3635, 2002     

A comparison of gas-phase methods of modifying polymer surfaces

Oxidation is the most common surface modification of polymers. This paper presents a comparison of five gas-phase surface oxidation processes: corona discharge, flame, remote air plasma, ozone, and combined UV/ozone treatments. Well-characterized biaxially oriented films of polypropylene and poly(ethylene terephthalate) were treated by each of the five techniques. The surface-treated films were then analyzed by X-ray photoelectron spectroscopy (XPS or ESCA), contact-angle measurements, and Fourier-transform IR (FTIR) spectroscopy. Corona, flame, and remote-plasma processes rapidly oxidize polymer surfaces, attaining XPS O/C atomic ratios on polypropylene of greater than 0.10 in less than 0.5 s. In contrast, the various UV/ozone treatments require orders of magnitude greater exposure time to reach the same levels of surface oxidation. While corona treatment and flame treatment are well known as efficient means of oxidizing polymer surfaces, the ability of plasma treatments to rapidly oxidize polymers is not as widely appreciated. Of the treatments studied, flame treatment appears to be the 'shallowest'; that is, the oxygen incorporated by the treatment is most concentrated near the outer surface of the film. Corona and plasma treatments appear to penetrate somewhat deeper into the polymers. At the other extreme, the UV/ozone treatments reach farther into the bulk of the polymers.     

Surface modification of atmospheric plasma activated BOPP by immobilizing chitosan

Summary Chitosan was immobilized onto plasma activated biaxially oriented polypropylene (BOPP) films aimed at producing antimicrobially active barrier film for food packaging applications. 1% chitosan dissolved into 0.1 M acetic acid was mixed with 0.1% glutaraldehyde (cross-linking agent) and applied onto N₂-plasma + NH₃ activated BOPP film. Amount of immobilized chitosan was 1.8 g/m². Films had strong antimicrobial activity against both Bacillus subtilis and Escherichia coli and they reduced the oxygen transmission rate (OTR) measured in dry conditions from 1500 down to 27 cm³/(m²·24 h). Migration tests for determining the total amounts of substances migrating into food simulants (3% acetic acid, 95% ethanol and iso-octane) indicated, that chitosan coating was permanently immobilized onto BOPP without any leaching (total migration < 2 mg/dm²), thus it met the requirements stipulated in Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with foodstuffs. The results suggest that chitosan treated BOPP films may be exploited in various food packaging applications requiring high oxygen barrier and/or antimicrobially active packaging materials.     

Oxygen plasma modification of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) film surfaces for tissue engineering purposes

Plasma glow‐discharge application is known as a technique to coat or modify the surfaces of various materials. In this study, the influence of oxygen rf‐plasma treatment on surface and bulk properties of a biological polyester, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), were studied by determining water content and water contact angle, and by using X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The plasma‐treated films absorbed more water than the untreated film, and the absorbance increased with the total power applied. The water contact angles decreased and O/C atomic ratio increased on treatment, indicating that the material became more hydrophilic due to increases in the oxygen‐containing functional groups on the surface of the polymer. A direct relation could be observed when the O/C ratio was plotted against the total power applied (treatment duration × treatment power). SEM revealed a visual record of surface modification, the extent of which increased with increased total power. It was thus possible to alter the surface chemistry and relevant properties of the polymer film using oxygen plasma as a tool. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1285–1289, 2003     

Surface modification of polymethyl methacrylate intraocular lenses with the mixture of acrylic acid and acrylamide via plasma‐induced graft copolymerization

An approach is presented for the graft copolymerization of acrylic acid (AAc) and acrylamide (AAm) mixture onto the surfaces of polymethyl methacrylate intraocular lenses (PMMA IOLs) treated with an Argon gas plasma, followed by the exposure to the oxygen atmosphere. In this case, peroxides formed by the plasma treatment are likely to be responsible for initiating the graft copolymerization. The amount of peroxides on the surface of PMMA IOLs was determined using 1,1‐diphenyl‐2‐picrylhydrazyl, and the maximum amount was found with the plasma treatment at 30 W for 20 s under 5 mTorr pressure. The surfaces of the grafted PMMA IOLs were characterized using Fourier transform infrared spectroscopy‐attenuated total reflectance (FTIR‐ATR), electron spectroscopy for chemical analysis, and contact angle meter. The FTIR‐ATR spectrum of PMMA‐g‐AAc‐AAm showed the characteristic band of PAAc at 1580 cm^?1 together with those of PAAm at 1670 and 1630 cm^?1, confirming that the copolymer of AAc and AAm was successfully grafted onto the surfaces of PMMA IOLs. The experimental data of O1s/C1s and N1s/C1s reasonably concurred with the calculated data, a strong indication that the pH value of the reaction medium at 3.77 could produce a graft with an equal molar ratio. Surface tension of the samples increased to 52 dyn/cm due to the graft of the hydrophilic monomers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2361–2366, 2002