Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Effect of ion implantation energy for the synthesis of Ge nanocrystals in SiN films with HfO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> stack tunnel dielectrics for memory application

Ge nanocrystals (Ge-NCs) embedded in SiN dielectrics with HfO₂/SiO₂ stack tunnel dielectrics were synthesized by utilizing low-energy (≤5 keV) ion implantation method followed by conventional thermal annealing at 800°C, the key variable being Ge⁺ ion implantation energy. Two different energies (3 and 5 keV) have been chosen for the evolution of Ge-NCs, which have been found to possess significant changes in structural and chemical properties of the Ge⁺-implanted dielectric films, and well reflected in the charge storage properties of the Al/SiN/Ge-NC + SiN/HfO₂/SiO₂/Si metal-insulator-semiconductor (MIS) memory structures. No Ge-NC was detected with a lower implantation energy of 3 keV at a dose of 1.5 × 10¹⁶ cm^-2, whereas a well-defined 2D-array of nearly spherical and well-separated Ge-NCs within the SiN matrix was observed for the higher-energy-implanted (5 keV) sample for the same implanted dose. The MIS memory structures implanted with 5 keV exhibits better charge storage and retention characteristics compared to the low-energy-implanted sample, indicating that the charge storage is predominantly in Ge-NCs in the memory capacitor. A significant memory window of 3.95 V has been observed under the low operating voltage of ± 6 V with good retention properties, indicating the feasibility of these stack structures for low operating voltage, non-volatile memory devices.     

Synthesis and properties of ultralow dielectric constant porous polyimide films containing trifluoromethyl groups

In this research, a series of porous copolyimide (co‐PI) films containing trifluoromethyl group (CF₃) were facilely prepared via a phase separation process. The co‐PI were synthesized by the reaction of benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride (BTDA) with two diamines of 4,4′‐diaminodiphenyl ether (ODA) and 3‐trifluoromethyl‐4,4'‐diaminodiphenyl ether (FODA) with various molar ratios. The flexible and tough porous co‐PI films with about 300 μm thickness and 8～10 μm average diameter could be obtained by solution casting conveniently. The thermal properties of the obtained porous co‐PI films were excellent with a glass transition temperature at 270 °C ～ 280 °C and only 5% weight loss in temperature from 530 °C to 560 °C under nitrogen atmosphere. In addition, the dielectric and hydrophobic properties of porous co‐PI films were remarkably improved owing to the presence of trifluoromethyl groups (CF₃) in the polymer chains. Moreover, our synthesized porous co‐PI films also showed good mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44494.     

A comparative study of the tribological behaviors of CH3- and CF3-terminated bilayer films

Two types of bilayer films were constructed on silicon substrates by a two-step self-assembly strategy. 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (TA) was chosen to create underlayer with amino-terminated surface, then n-octanoic acid (nOA) and perfluorooctanoic acid (PFOA) were chemically grafted to the amino-derivatized substrates, respectively, to construct CH₃- or CF₃-terminated bilayer film, denoted as TA–nOA and TA–PFOA, respectively. The formation and surface properties of the films were evaluated by ellipsometry, contact angle goniometers, X-ray photoelectron spectroscopy, and atomic force microscope (AFM). The nano- and micro-tribological properties of TA–nOA and TA–PFOA bilayers were comparatively investigated via AFM and ball-on-plate tribometer, respectively. Results show that these two types of bilayer films exhibit good anti-adhesive and friction-reducing properties, and TA underlayer enhances the stability of these films through interchain hydrogen bonding. At nanoscale, TA–PFOA film exhibits lower adhesion and friction force because of –CF₃ terminals with lower work of adhesion. However, the micro-tribological property of TA–PFOA is inferior to that of TA–nOA film. This could be attributed to the fact that –CF₃ terminal groups with larger size tend to form less-ordered structure. Moreover, larger terminal groups lead to more energy dissipation during sliding.     

One‐step fabrication of fluoropolymer transparent films with superhydrophobicity by dry method

Fluoropolymer transparent thin films were deposited on different substrates by one‐step vacuum evaporation method, which exhibit superhydrophobic property with water contact angle (CA) greater than 150°. Polytetrafluoroethylene (PTFE) film with network structure shows high oleophobicity with oil CA of 138°, whereas polytetrafluoroethylene‐perfluoropropylvinylethers (PFA) film with particle structure is superoleophilicity with oil CA near 0°. It is believed that different conformation of  CF₂ groups at the surface lead to this different surface activity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Surface characterization of polymers modified by keV and MeV ion beams

The present work deals with two different surface modification techniques for altering the surface properties of polymers: plasma treatment and ion implantation. Polymer foils were exposed in an inductively-coupled r.f. (13.56 MHz) plasma system with and without applying a negative high voltage pulse to the sample stage. The influence of low pressure plasmas of oxygen, nitrogen, or argon on the chemical composition, topography, and wettability of polymer surfaces was studied in detail. Etch rates of poly(ethylene terephthalate) for different plasma parameters were monitored. The polymer surface was also modified by a high energy ion beam process. Polyimide films were implanted with different ion species such as Ar⁺, N⁺, C⁺, He⁺, and O⁺ at doses from 1 × 10¹⁵ to 1 × 10¹⁷ ion/cm². Ion energy was varied from 10 to 60 keV for the plasma source ion implantation (PSII) experiment. Polyimide samples were also implanted with 1 MeV hydrogen, carbon, and oxygen ions at a dose of 1 × 10¹⁴ ion/cm². Depending on the ion energy, dose, and ion species, the surface resistivity of the film was reduced by several orders of magnitude. A study on the plasma-treated and ion beam-treated polymer surfaces was performed using TOF-SIMS, XPS, SEM, AFM, and water contact angle measurements.     

Ion beam irradiation effect on gas permeation properties of polyimide films

This study deals with the ion beam irradiation effect on gas permeation properties of polyimide films. 2 MeV α, 500 keV, and 170 keV N⁺ ions were used for modifying the membranes. It was found that there are two different effects according to the implantation dose. In the case of small-dose irradiation, ion implantation causes a raise of permeability both for CH₄ and H₂. When the implantation dose reaches a more important level, the implanted membranes have at the same time high permselectivity for H₂/CH₄ and high permeability for H₂. The relationships between the permeation properties and microstructure of the films are also discussed. © 1995 John Wiley & Sons, Inc.     

Creating Stable Hydrophobic Surfaces by Poly(butyl methacrylate) End-Capped with 2-perfluorooctylethyl Methacrylate Units

Summary It is a challenge to fabricate fluorine-containing polymer surface with low-energy properties and superior long-lasting barrier properties as well as lower fluorine content. In this paper, poly(butyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate units (PBMA-ec-FMA) , having the so-called push-me/pull-you structures, have been synthesized by ATRP and their surface properties were investigated. This structure was in favorable of the longer -(CF₂)₇CF₃moieties self-assembling on the polymer surface during film formation, which resulted in better chain alignment and packing of the longer -(CF₂)₇CF₃moieties. Therefore, the contact angles of water and paraffin oil on the surface of the end-capped PBMA were 118° and 84°, respectively, approaching that of poly(2-perfluorooctylethyl methacrylate) homopolymer, even though the content of FMA was 0.34 mol% (the average polymerization degree of PFMA units is 1). However, more than 9 mol% was necessary for the relative random copolymer (PBMA-r-PFMA) to reach these values of the contact angle. Regardless of the wetting properties, the end-capped PBMA by fluorinated methacrylate has better resistance to surface reconstruction than PBMA-r-PFMA random copolymer even though FMA content in PBMA-ec-FMA is much lower than that in random copolymer. Therefore, it may be a facile method to create stable hydrophobic surfaces with lower price.     

Porous poly(L‐lactic acid)/poly(ethylene glycol) blend films

Poly(L ‐lactic acid) (PLLA: M_w = 19.4 × 10⁴)/poly(ethylene glycol) (PEG: M_w = 400) blend films were formed by use of a solvent‐cast technique. The properties and structures of these blend films were investigated. The Young's modulus of the PLLA decreased from 1220 to 417 MPa with the addition of PEG 5 wt %, but the elongation at break increased from 19 to 126%. The melting point of PLLA linearly decreased with increases in the PEG content (i.e., pure PLLA: 172.5°C, PLLA/PEG = 60/40 wt %: 159.6°C). The PEG 20 wt % blend film had a porous structure. The pore diameter was 3–5 μm. The alkali hydrolysis rate of this blend film was accelerated due to its porous structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 965–970, 2004     

Fabrication of fluorine-terminated diamond-like carbon thin film using a hyperthermal atomic fluorine beam

Surface modification of diamond-like carbon (DLC) film was performed using a hyperthermal atomic fluorine beam on the purpose of production of hydrophobic surface by maintaining the high hardness of DLC film. By the irradiation of atomic fluorine beam of a 1.0 × 10²⁰ atoms/cm², the contact angle of a water drop against the DLC surface increased from 73° to 111°. The formation of CF₃, CF₂ and CF bonding on the modified DLC surface was confirmed from the measurements of X-ray photoelectron spectra and near-edge X-ray absorption fine structure spectra. Irradiation of hyperthermal atomic fluorine beam was concluded to produce insulator fluorine-terminated DLC film, which has high F content on the surface, by the taking of the use of neutral atomic beam as a fluorine source.     

Properties of films obtained by UV-curing 4,4'-hexafluoroisopropylidenediphenoldihydroxyethylether diacrylate and its mixtures with the hydrogenated homologue

A new ultraviolet (UV)-curable acrylic monomer, 4,4'-hexafluoroisopropylidene-diphenoldihydroxyethylether diacrylate, was synthesized: it was cured as a film and its properties compared with those of its fully hydrogenated homologue. The introduction of two CF₃groups into the monomer did not change its reactivity in the UV-curing reaction, but increased the glass transition temperature (T_g) of the cured polymeric film, decreased its refractive index (n), and lowered its surface tension. The fluorinated and the hydrogenated monomers were completely miscible and give homogeneous films: the T_g and n values were found linearly dependent on the fluorinated monomer content. The surface properties were deeply influenced by the presence of fluorine; a surface enrichment of the fluorinated monomer was evidenced by X-ray photoelectron spectroscopy analyses on the surfaces of the films obtained from mixtures of the two monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 979–983, 1997     

Surface morphology of PECVD fluorocarbon thin films from hexafluoropropylene oxide, 1,1,2,2‐tetrafluoroethane,and difluoromethane

Atomic force microscopy (AFM) measurements have been made on a series of fluorocarbon films deposited from pulsed plasmas of hexafluoropropylene oxide (HFPO), 1,1,2,2‐tetrafluoroethane (C₂H₂F₄), and difluoromethane (CH₂F₂). All of the films give images showing nodular growth (cauliflower‐like appearance), with the size and distribution of the nodules dependent on both the precursor, the degree of surface modification to which the growing film is exposed, and the substrate surface. Films deposited from C₂H₂F₄ showed clusters of smaller nodules around larger nodules, whereas films deposited from CH₂F₂ were characterized by a uniform distribution of smaller nodules, and films deposited from HFPO had the largest observed nodules. Movchan and Demchishin's structure zone model was applied to the observed films, which were all found to be zone 1 structures, indicating that film growth is dominated by shadowing effects. Increased substrate temperature and incident power per nm of film deposited results in decreased rms roughness, consistent with greater atomic mobility during deposition. Larger nodules in the fluorocarbon films developed on silicon wafer substrates than on rougher Al‐coated substrates. Advancing contact angles for all of the films were found to be higher than that of PTFE (108°), indicating both hydrophobic and rough surfaces. Specifically, contact angles of films deposited from HFPO were found to increase with pulse off‐time, the same trend observed for both the CF₂ fraction of the film and the rms roughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2439–2447, 1999     

Oxygen barrier properties of polyketone/EVOH blend films and their resistance to moisture

Polyketone (PK) has excellent chemical and mechanical properties, but its use in food packaging is limited due to its oxygen barrier properties being insufficient for high-barrier film applications. To improve its oxygen barrier properties, PK has been blended with ethylene vinyl alcohol copolymer (EVOH), which is one of the highest oxygen barrier polymers in use today. The oxygen barrier properties under both dry and humid conditions, as well as the mechanical properties of PK/EVOH blend films were investigated in this study. These novel PK/EVOH blend films exhibited unusually low oxygen permeability values from 0.3 to 0.16 cc 20 μm m⁻² day⁻¹ atm⁻¹ with increasing EVOH content from 30 to 70 wt%, which are even lower than those of the ideal laminar model that expresses the theoretical minimum permeability values attainable for blended barrier films. These high oxygen barrier properties of PK/EVOH blend films can conceivably be attributed to the combination of two dominant effects: a tortuous diffusion path through the EVOH domains in the PK matrix and hydrogen bonding interactions between PK and EVOH. Furthermore, in high-humidity environments with retorting, the PK/EVOH blend films exhibited superior resistance to moisture over EVOH. Immediately after the retorting test, the oxygen permeability of the high-barrier PK/EVOH blend films with an EVOH content of 30–40 wt% increased by less than 3× the pre-retorting value, as opposed to 74× for EVOH. In addition, PK/EVOH blend films displayed superior stretching characteristics, with a breaking strain of over 300%, which are valuable for flexible packaging applications.     

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     

Surface hydrophilicity and enzymatic hydrolyzability of biodegradable polyesters: 1. effects of alkaline treatment

Surface treatment using alkaline solutions was attempted to enhance the surface hydrophilicity and enzymatic hydrolyzability of hydrophobic poly(L ‐lactide) [ie poly(L ‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL). The alkaline treatment was performed by immersing the PLLA and PCL films in 0.01 and 4 N NaOH solutions, respectively, for various periods of time. The effects of the alkaline treatment on the hydrophilicity of the films were monitored by dynamic contact angle measurements, while the enzymatic hydrolyzability of the PLLA and PCL films after the alkaline treatment were evaluated by weight losses in the presence of proteinase K and Rhizopus arrhizus lipase, respectively. With the alkaline treatment the hydrophilicity of the PLLA and PCL films was controllable in the advancing contact angle (θ_a) ranges of 84–108° and of 69–93°, respectively, by varying the alkaline treatment time. The enzymatic hydrolysis rates of the PLLA films became higher with decrease of the θ_a, irrespective of the crystallinity, strongly suggesting that the surface hydrophilicity or the surface molecular weight is crucial to determine their enzymatic hydrolyzability. In contrast, the enzymatic hydrolyzability of the PCL films remained unchanged even when the θ_a decreased from 93° to 73° by alkaline treatment for 4 h. However, prolonged alkaline treatment for periods of time exceeding 4 h, which insignificantly altered the θ_a but caused the formation of pores and cracks on the PCL film surface, accelerated the enzymatic hydrolysis of the PCL films. This indicates that the enzymatic hydrolyzability of the PCL film depends on the surface area per unit weight rather than the surface hydrophilicity. Copyright © 2003 Society of Chemical Industry     

Oxygen barrier and enthalpy of melting of multilayer EVOH films after pressure‐assisted thermal processing and during storage

Pressure‐assisted thermal processing (PATP) is an advanced thermal process involving application of elevated pressures above 600 MPa on a preheated food for a holding time of 3 to 5 min, causing the volumetric temperature of food to increase above 100°C, to inactivate bacterial spores and enzymes. This study evaluated the influence of PATP on two state‐of‐the‐art multilayer EVOH films. Flexible pouches containing water as the food simulant were made from the two films and processed at 680 MPa for 3 min at 105°C and 680 MPa for 5 min at 100°C. Each film was investigated for its oxygen transmission rates (OTRs), melting temperature (T_m), enthalpy of melting (ΔH), and overall crystallinity before (control) and after processing. The changes in OTRs and total ΔH of the two films were also analyzed during a storage period of 240 days in ambient conditions after processing. Results showed a significant (P < 0.05) increase in the OTRs of the two films after PATP. However, PATP did not cause a significant (P > 0.05) change in the T_m and ΔH of the two films. The overall crystallinity of film A decreased, but improved slightly for film B after PATP. A recovery in the OTRs of the two films occurred during storage. The films also showed changes in the total ΔH measured during the storage period, which was used to explain the changes in the oxygen barrier properties. The OTR of both films remained below 2 cc/m² day, which is required in packaging applications for shelf‐stable foods with a 1‐year shelf life. This work demonstrates the advantages of using multilayer films containing EVOH as the barrier layer in PATP applications to produce shelf‐stable foods. This work also highlights the advantage of, DSC analysis for studying the physical ageing of polymers during storage. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Linking morphology changes to barrier properties of polymeric packaging for microwave‐assisted thermal sterilized food

It is a priority to develop polymeric packaging that can withstand microwave‐assisted thermal sterilization (MATS) and maintain the quality of low‐acid foods during long‐term storage. In this study, we explored changes in the morphology of pouch films with two multi‐layer structures. The films are based on barrier layers of metal oxide‐coated poly(ethylene terephthalate) (PET) (film A) and ethylene vinyl alcohol (EVOH) (film B). A 8‐oz model food in pouches was processed with MATS (F₀ = 9.0 min) and stored at 23, 35 and 45 °C for up to 12 months. Findings reveal that the oxygen barrier of film A was influenced by the coating and crystallinity of PET. The oxygen barrier of film B was primarily affected by the moisture content of the EVOH polymer. Results also show that changes in barrier properties depended on storage temperature. Recrystallization in polymer might be an important morphological change that occurs during storages. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45481.     

Film growth and relationship between microstructure and mechanical properties of a-C:H:F films deposited by PECVD

Results of a systematic investigation on the effects of some deposition parameters (partial pressure of CF₄ and self-bias voltage) on the microstructure, mechanical and tribological properties of a-C:H:F films are presented. The films were deposited by r.f.-PECVD using CH₄–CF₄ mixtures. The film composition was measured by ion beam analysis and, combining these results with the film thickness, the film density was determined. The structural arrangement was probed by Raman spectroscopy and the chemical bonding was investigated by infrared absorption and X-ray photoelectron spectroscopies. The hardness was measured by microindentation and the internal stress was determined by measuring the changing of the substrate curvature after the film deposition. The friction coefficient was measured by lateral force microscopy. The results indicate that the properties of a-C:H:F films are controlled by the ionic bombarding during the film growth. For a fixed self-bias, the increase of the CF₄ partial pressure leads to a transition from diamond-like to a polymer-like structure, to a higher fluorine incorporation and to a decrease of both hardness and internal stress. The friction coefficient decreases too. The fluorine incorporation also increases with the increase of the self-bias and was associated to higher plasma decomposition. Fluorine-poor polymer-like films were deposited at low self-bias (−50 V). In both situations, fluorine incorporation occurs at the expenses of the hydrogen content and the reduction of the energy of the bombarding species results in less dense and soft films with a polymer-like structure.