Effects of aromatic groups in polymer chains on plasma surface modification

Three polyester films with different repeating units—poly(lactic acid) (PLA), poly(ethylene terephthalate) (PET), and poly(oxybenzoate‐co‐oxynaphthoate) (PBN)—were modified by plasma, and the way in which the chemical compositions of the polymer chains influenced the plasma modification was investigated with contact‐angle measurements and X‐ray photoelectron spectroscopy (XPS). There were large differences in the compensated rates of weight loss among the three polyester films when they were exposed to Ar and O₂ plasmas. The PLA film showed the highest rate for weight loss of the three films, and the PBN film showed the lowest rate. The PET and PBN film surfaces were modified to become more hydrophilic by either argon or oxygen plasma. However, the PLA film surface was not made more hydrophilic by the plasmas. XPS spectra showed that the PLA film surface was not modified in its chemical composition, but the PBN film surface was modified in its chemical composition to form C? O groups in the PBN polymer chains. The reason that the PLA film surface was not modified but the PBN film surface was modified was examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 96–103, 2003     

Improvement of Adhesion Between Liquid Crystalline Polyester Films by Plasma Treatment

Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was carried out by low-pressure plasma treatment to improve the initial adhesion as well as the long-term adhesion reliability, a measure of durability between the LCP films used as substrates for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes such as reactive-ion-etching, and direct-plasma (DP) with pressures ranging from 6.7 Pa to 26.6 Pa. The introduction of polar groups on the film surface such as phenolic hydroxyl groups and carboxyl groups enhanced the initial adhesion by increased chemical interaction. However, if the concentration of polar groups became too high, the longterm adhesion reliability estimated by the pressure cooker test was degraded due to the acceleration of the penetration of water molecules into the interface. A large surface roughness was also effective in preventing the decrease in the long-term adhesion reliability. However, too much increase in surface roughness decreases the long-term adhesion reliability. The DP-treatment in the O₂ atmosphere at a gas pressure of 6.7 Pa was found to be the best plasma condition for both the initial adhesion as well as the long-term adhesion reliability between the LCP films.     

Surface modification of polytetrafluoroethylene films by plasma pretreatment and graft copolymerization to improve their adhesion to bismaleimide

BACKGROUND: Polytetrafluoroethylene (PTFE) is utilized in many engineering applications, but its poor wettability and adhesion properties with other materials have limited its use. The study reported was aimed at achieving surface modification of PTFE films by radiofrequency NH₃ and N₂ plasma treatment, followed by graft copolymerization, in order to improve the interfacial adhesion of PTFE and bismaleimide. RESULTS: X‐ray photoelectron spectroscopy results showed that a short‐time plasma treatment had a distinct defluorination effect and led to nitrogen functional group formation. The nitrogen chemical bonding form was different for NH₃ and N₂ plasma treatments. Under the same experimental conditions, the NH₃ plasma exhibited a better etching effect than did the N₂ plasma. Contact angle measurement showed an improvement in both surface energy and wettabliity by short‐time plasma treatment. The concentration of the surface‐grafted bismaleimide on PTFE increased after the plasma pretreatment. The lap shear strength between PTFE and bismaleimide increased significantly after surface modification. CONCLUSION: This study found that plasma treatment caused changes in surface chemistry, thus leading to an increase of the wettability of PTFE surfaces. Hence, the adhesion properties of PTFE with bismaleimide were significantly improved. Copyright © 2008 Society of Chemical Industry     

Plasma surface modification of polyimide for improving adhesion to electroless copper coatings

The influences of oxygen plasma treatment of polyimide (PI) films on the adhesion of electroless copper coatings as well as on the chemical composition of the film surface and the PI surface morphology were investigated. The plasma operating parameters were 1800 W forward power with O₂ flowing at a rate of 300 cm³/min at a pressure of 200 mTorr. The peel strength increased with decreasing plasma treatment temperature. However, extension of the treatment time at higher temperatures had a positive effect on adhesion. A correlation between the enhancement in peel strength and the content of oxygen-containing groups at the PI surface (investigated using XPS) was observed. A change in the morphology as a result of plasma etching was also observed, in the formation of pits in the film surface. The pits ranged from 3 to 6 μm in depth and the diameter varied from 10 to 200 μm. Comparison of the data obtained after plasma treatment with the results of chemical etching in alkaline solutions of permanganate showed approximately the same adhesion increase (to 0.6 kN/m) in both cases. However, chemical etching did not affect the surface morphology and increased the oxygen content at the PI surface less than the plasma treatment.     

Role of polymer chain end groups in plasma modification for surface metallization of polymeric materials

How to improve adhesion between poly(oxybenzoate‐co‐oxynaphthoate) (Vecstar OC and FA films) and copper metal by Ar, O₂, N₂ and NH₃ plasma modification was investigated. The mechanism of adhesion improvement is discussed from the viewpoint of chemical and physical interactions at the interface between the Vecstar film and copper metal layer. The adhesion between Vecstar OC film and copper metal was improved by chemical rather than physical interactions. Polymer chain end groups that occur at Vecstar OC film surfaces contribute effectively to adhesion. This improvement in adhesion is due to interactions between copper metal and O?C groups formed by plasma modification. Aggregation of the O?C groups to the copper metal/Vecstar OC film interface is a key factor for good adhesion. From this aspect, heat treatment of plasma‐modified Vecstar OC films on glass plates is effective in the aggregation, and the peel strength for the copper metal/Vecstar OC film system reached 1.21 N (5 mm)^?1. Copyright © 2009 Society of Chemical Industry     

Fabrication of superhydrophobic polylactide films with ultraviolet-shielding properties

ZnO is a useful material with stable physical and chemical properties for introducing surface roughness and UV-blocking properties. However, to inhibit ZnO particles’ photocatalytic degradation of peripheral organic materials, we conducted layer-by-layer (LbL) deposition with poly(sodium 4-styrenesulfonate) and poly(diallyl dimethyl ammonium chloride) to fabricate ZnO particles with an SiO₂ shell with tetraethyl orthosilicate. Polylactide (PLA) films were prepared by compression molding and treated with a weak alkali solution for 0.5, 1.0, 1.5, and 2.0 h to induce hydroxyl and carboxyl groups. The LbL deposition of polyelectrolytes on the PLA film was performed to induce electrical interactions between the PLA films and ZnO composite particles. ZnO composite particles were deposited onto the surface of the PLA films with dip coating, and a stable superhydrophobic surface was developed after hexadecyl trimethoxysilane treatment via a reduction in the surface energy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47760.     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Surface Characterization of Plasma Treated Carbon Fibers and Adhesion to a Thermoplastic Polymer

The surface chemistry of IM7 carbon fibers was characterized by x-ray photoelectron spectroscopy (XPS). The fiber surface energetics were determined from a two-liquid tensiometric method. The adhesion between as-received and plasma-treated carbon fibers and polyethersulfone (PES) was measured by the microbond pull-out test.

The surface characterization techniques showed that the effect of any plasma treatment is attained within less than 15 seconds. It was found that both argon and air plasmas increased the oxidation state of the fiber surface and that they reduced the dispersive component (γ_s ^d) of the fiber surface free energy considerably. The ammonia plasma treatment resulted in a cleaning of the surface. This plasma treatment was also effective in improving the fiber/matrix adhesion of quenched samples. A similar adhesion enhancement between as-received fibers and PES is obtained by annealing the samples above the Tg of the polymer. The air plasma treatment did not have any significant effect on the fiber/matrix adhesion.     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

Structure,gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.     

Amination of Polymeric Braid Structures to Improve Tendon Healing: An Experimental Comparison

Several polymers are researched for tendon repair as polyethylene terephthalate (PET) and polylactic acid (PLA). These are biocompatible and useful in scaffolding repair though with minimal success due to long-term failure. There is a need to improve such scaffolds' design and physical–chemical nature. This work concerns surface functionalization of polymeric braids (PET and PLA) that fulfill the high mechanical demands of tissues such as tendons. The functionalization aims to incorporate amine groups in the braids' surface, improve cell adhesion, and consequently, the poor healing rate of these tissues and the biointegration of the braids. Two approaches are compared: the direct application of NH₃ plasma and the surface grafting of EDA after O₂ plasma activation. X-ray photoelectron spectroscopy (XPS) shows that amine groups are effectively introduced onto the samples' surfaces. Besides, the plasma parameters chosen do not compromise the topography and tensile behavior of the braids. Resazurin assay and scanning electron microscopy show that the NH₃ treatment improves cell–biomaterial interaction as improved cell adhesion and proliferation are observed. Both approaches are safe for biomedical applications. The NH₃ plasma approach is more environmentally friendly, faster, and easier to scale-up, showing potential for application in the final hybrid medical device.     

Morphology and glass transition of thin polylactic acid films

The aim of this study is to highlight the effect of the morphology of polylactic acid (PLA) thin films on the glass transition in this confined geometry. For that purpose, poly(L ‐lactic acid) and poly(D ‐lactic acid) polymer films were prepared on different surfaces such as mica and silicon surfaces by using two different solvents. The films exhibit different morphologies starting from individual macromolecular chains at very low concentration to homogeneous films at higher concentrations. Globular to elongated rodlike structures of the PLA macromolecules were observed according to the polarity of the surface and the solvent. The T_g of PLA enantiomeric film, determined by adhesion force using atomic force microscopy (AFM) as a function of temperature, was confirmed by ellipsometric measurements. Surprisingly, this value is independent of the morphology of thin enantiomeric film. A balance between the attractive surface effects and a decrease of the crystallinity of PLA on the mobility in the amorphous region will be discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Degradation properties of PLA and PHBV films treated with CO2-plasma

The objectives of this study are to investigate the effects of an inductively coupled CO₂-plasma treatment on two biodegradable PLA and PHBV films and to confirm the possibility of improving the degradation properties in variety of solutions. X-ray photoelectron spectroscopy and contact angle measurement were employed to analyze the surface chemical states and to observe specific chemical changes on the surfaces. To study biodegradation, three acidic, neutral, and basic solutions were prepared, respectively. After the plasma treatment and the degradation test, scanning electron microscopy was also employed to observe the surface morphologies of the films. In conclusion, the exposure of the polymer surfaces to CO₂-plasma could encourage the formation of polar groups and oxidation on the surfaces, thereby increasing the roughness, wettability, and degradability of the surfaces.     

Polylactic acid nanocomposites toughened with nanofibrillated cellulose: microstructure,thermal, and mechanical properties

Structure–property interdependency is of vital importance in developing advanced polymer nanocomposites as well as enhancing their ultimate properties. In this research study, toughening of polylactic acid (PLA) with nanofibrillated cellulose (NFC) was studied and comparison was made between the thermal and mechanical properties of systems containing pristine and modified NFC. NFC was modified through two different methods: acetylation of hydroxyl groups and grafting of poly(ethylene glycol) (PEG) onto cellulose chains. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry were employed to probe into the surface characteristics, thermal properties, and crystallinity of NFC/modified NFC, respectively; moreover, SEM imaging was utilized for surface morphology of the samples. Subsequently, PLA with modified and unmodified NFC was prepared to evaluate the filler addition effect on toughness. Acetylated NFC has changed the PLA crystallinity degree and rate, which affected the modulus of PLA, as signaled by the changed NFC surface. Particularly, mechanical and toughening behaviors of the prepared nanocomposites were analyzed based on tensile measurements which showed an eightfold rise in toughening along with 18% decrease in modulus of the samples comprising 1 wt% of acetylated NFC compared to a blank PLA. However, a sevenfold increase in toughening was observed upon introduction of both modified NFC to the PLA matrix. SEM observations divulged proper dispersion of NFC-g-AC in the PLA matrix which reduced stress concentration, but enhanced toughness in comparison with NFC-g-PEG with agglomeration that caused stress concentration leading to brittle behavior. In the light of the obtained results, it can be inferred that brittle PLA can be toughened by the surface-modified NFC. This research study can illuminate the way for future works on the modifications of nano-scale fillers/additives to achieve improved mechanical and thermal properties of PLA.     

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     

Preparation of oxygen gas barrier polypropylene films by deposition of SiOx films plasma‐polymerized from mixture of tetramethoxysilane and oxygen

Silicon oxide (SiOx) film deposition on the surface of oriented poly(propylene) (OPP) films was done to form a new oxygen gas barrier material using plasma polymerization of the tetramethoxysilane (TMOS)/O₂ mixture. The SiOx film deposition on OPP films never improved oxygen gas barrier properties. The inefficacy of the SiOx deposition was due to poor adhesion at the interface between the deposited SiOx and OPP films and also to the formation of cracks in the deposited SiOx film. If prior to the SiOx film deposition surface modification of OPP films was done by a combination of the argon plasma treatment and TMOS coupling treatment, this contributed effectively to strong adhesion leading to success in the SiOx deposition on the OPP film surface, and then the oxygen gas barrier ability was improved. The oxygen permeation rate through the SiOx‐deposited OPP film was decreased from 2230 to 37–52 cm³/m²/day/atm, which was comparable to that of poly(vinylidene chloride), 55 cm³/m²/day/atm at a film thickness of 11 μm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2389–2397, 2000     

Ta and TaN adhesion to high-temperature fluorinated polyimides. Surface and interface chemistry

The practical adhesion of Cu/Ta to high-temperature fluorinated polyimides (FPIs) was initially good but failed after the reliability test involving treatment under the FPI curing condition five times (T₅). But a thin layer (40 nm) of TaN greatly improved the reliability of the Cu/Ta-to-FPI adhesion. Both CF₄ and in situ Ar plasma treatments of FPIs prior to metal deposition enhanced the metal-to-FPI adhesion strength. CF₄ plasma enriches the FPI surface with fluorine atoms and most of fluorine is bound to carbon as CF₃, CF₂, and CF. Ar plasma first destroys CF₃ and then C=O groups of the FPIs to yield a polar surface. The locus of failure by a 90° peel test was found to be within the Ar-plasma-modified FPI layer but it moved toward the bulk of FPI, i.e. away from the metal-polymer interface, after the T₅ reliability test. The locus of failure in the case of weak adhesion where no plasma treatment was done on FPI films was in the near-interface region within the FPI layer, and the failure seemed to occur in the weak boundary layers of FPI surfaces. Plasma treatment removes weak boundary layers and also increases FPI surface roughness. These two effects combined improved the metal-to-FPI practical adhesion.     

Plasma surface modification of poly(phenylene sulfide) films for copper metallization

Poly(phenylene sulfide) (PPS) films were modified by Ar, O₂, N₂ and NH₃ plasmas in order to improve their adhesion to copper metal. All four plasmas modified the PPS film surfaces, but the NH₃ plasma modification was the most effective in improving adhesion. The NH₃ plasma modification brought about large changes in the surface topography and chemical composition of the PPS film surfaces. The peel strength for the Cu/plasma-modified PPS film systems increased linearly with increasing surface roughness, R _a or R _rms, of the PPS film. The plasma modification also led to considerable changes in the chemical composition of the PPS film surfaces. A large fraction of phenylene units and a small fraction of sulfide groups in the PPS film surfaces were oxidized during the plasma modification process. Nitrogen functional groups also were formed on the PPS film surfaces. The NH₃ plasma modification formed S—H groups on the PPS film surfaces by reduction of S—C groups in the PPS film. Not only the mechanical interlocking effect but also the interaction of the S—H groups with the copper metal may contribute to the adhesion of the Cu/PPS film systems.     

XPS/AFM study of the PET surface modified by oxygen and carbon dioxide plasmas: Al/PET adhesion

The formation of the interface between aluminium and O₂ or CO₂ plasma-modified poly(ethylene terephthalate) (PET) has been investigated by X-ray photoelectron spectroscopy (XPS). As demonstrated by the changes in the C 1s, O 1s, and A1 2p core level spectra upon A1 deposition, the metal was found to react preferentially with the original ester, with the plasma-induced carboxyl and carbonyl groups to form interfacial complexes. The phenyl ring at the modified PET surface was seen to be involved in the formation of the interface, but to a lesser extent. This confirms the high reactivity of the oxygen-containing groups towards the deposited A1 atoms. The adhesion between A1 and the plasma-modified PET films was evaluated by means of a 180° peel test. A considerable (up to ten times) improvement in adhesion was achieved by plasma treatment of the PET substrate, but for either plasma gas the adhesion strength was found to depend strongly on the plasma power and treatment time. The results are discussed in terms of the concentration of oxygen-containing groups at the polymer surface, the surface topography, and the possible presence of low-molecular-weight materials at the metal-polymer interface.     

Preparation and properties of polylactide–silica nanocomposites

Poly(lactic acid) (PLA)/SiO₂ nanocomposites were prepared via melt mixing with a Haake mixing method. To improve the dispersion of nanoparticles and endow compatibility between the polymer matrix and nanosilica, SiO₂ was surface‐modified with oleic acid (OA). The interfacial adhesion of the PLA nanocomposites was characterized by field‐emission scanning electron microscopy. The storage modulus and glass‐transition temperature values of the prepared nanocomposites were measured by dynamic mechanical thermal analysis. The linear and nonlinear dynamic rheological properties of the PLA nanocomposites were measured with a parallel‐plate rheometer. The effects of the filling content on the dispersability of the OA–SiO₂ nanoparticles in the PLA matrix, the interface adhesion, the thermomechanical properties, the rheological properties, and the mechanical properties were investigated. Moreover, the proper representation of the oscillatory viscometry results provided an alternative sensitive method to detect whether aggregation formed in the polymeric nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010